I had the same issue and found lots of similar questions out there, but no good examples on how to do it. The following is what I did with Xerces-for-Android to get my stuff to work. Good luck :)
The following worked for me:
- Create a validation utility.
- Get both the xml and xsd into file on the android OS and use the validation utility against it.
- Use Xerces-For-Android to do the validation.
Android does support some packages which we can use, I created my xml validation utility based on: http://docs.oracle.com/javase/1.5.0/docs/api/javax/xml/validation/package-summary.html
My initial sandbox testing was pretty smooth with java, then I tried to port it over to Dalvik and found that my code did not work. Some things just aren't supported the same with Dalvik, so I made some modifications.
I found a reference to xerces for android, so I modified my sandbox test of (the following doesn't work with android, the example after this does): 
import java.io.File;
import javax.xml.XMLConstants;
import javax.xml.parsers.DocumentBuilder;
import javax.xml.parsers.DocumentBuilderFactory;
import javax.xml.transform.Source;
import javax.xml.transform.dom.DOMSource;
import javax.xml.transform.stream.StreamSource;
import javax.xml.validation.Schema;
import javax.xml.validation.SchemaFactory;
import javax.xml.validation.Validator;
import org.w3c.dom.Document;
/**
 * A Utility to help with xml communication validation.
 */
public class XmlUtil {
    /**
     * Validation method. 
     * Base code/example from: http://docs.oracle.com/javase/1.5.0/docs/api/javax/xml/validation/package-summary.html
     * 
     * @param xmlFilePath The xml file we are trying to validate.
     * @param xmlSchemaFilePath The schema file we are using for the validation. This method assumes the schema file is valid.
     * @return True if valid, false if not valid or bad parse. 
     */
    public static boolean validate(String xmlFilePath, String xmlSchemaFilePath) {
        // parse an XML document into a DOM tree
        DocumentBuilder parser = null;
        Document document;
        // Try the validation, we assume that if there are any issues with the validation
        // process that the input is invalid.
        try {
            // validate the DOM tree
            parser = DocumentBuilderFactory.newInstance().newDocumentBuilder();
            document = parser.parse(new File(xmlFilePath));
            // create a SchemaFactory capable of understanding WXS schemas
            SchemaFactory factory = SchemaFactory.newInstance(XMLConstants.W3C_XML_SCHEMA_NS_URI);
            // load a WXS schema, represented by a Schema instance
            Source schemaFile = new StreamSource(new File(xmlSchemaFilePath));
            Schema schema = factory.newSchema(schemaFile);
            // create a Validator instance, which can be used to validate an instance document
            Validator validator = schema.newValidator();
            validator.validate(new DOMSource(document));
        } catch (Exception e) {
            // Catches: SAXException, ParserConfigurationException, and IOException.
            return false;
        }     
        return true;
    }
}
The above code had to be modified some to work with xerces for android (http://gc.codehum.com/p/xerces-for-android/). You need SVN to get the project, the following are some crib notes:
download xerces-for-android
    download silk svn (for windows users) from http://www.sliksvn.com/en/download
        install silk svn (I did complete install)
        Once the install is complete, you should have svn in your system path.
        Test by typing "svn" from the command line.
        I went to my desktop then downloaded the xerces project by:
            svn checkout http://xerces-for-android.googlecode.com/svn/trunk/ xerces-for-android-read-only
        You should then have a new folder on your desktop called xerces-for-android-read-only
With the above jar (Eventually I'll make it into a jar, just copied it directly into my source for quick testing. If you wish to do the same, you can making the jar quickly with Ant (http://ant.apache.org/manual/using.html)), I was able to get the following to work for my xml validation:
import java.io.File;
import java.io.IOException;
import mf.javax.xml.transform.Source;
import mf.javax.xml.transform.stream.StreamSource;
import mf.javax.xml.validation.Schema;
import mf.javax.xml.validation.SchemaFactory;
import mf.javax.xml.validation.Validator;
import mf.org.apache.xerces.jaxp.validation.XMLSchemaFactory;
import org.xml.sax.SAXException;
/**
 * A Utility to help with xml communication validation.
 */public class XmlUtil {
    /**
     * Validation method. 
     * 
     * @param xmlFilePath The xml file we are trying to validate.
     * @param xmlSchemaFilePath The schema file we are using for the validation. This method assumes the schema file is valid.
     * @return True if valid, false if not valid or bad parse or exception/error during parse. 
     */
    public static boolean validate(String xmlFilePath, String xmlSchemaFilePath) {
        // Try the validation, we assume that if there are any issues with the validation
        // process that the input is invalid.
        try {
            SchemaFactory  factory = new XMLSchemaFactory();
            Source schemaFile = new StreamSource(new File(xmlSchemaFilePath));
            Source xmlSource = new StreamSource(new File(xmlFilePath));
            Schema schema = factory.newSchema(schemaFile);
            Validator validator = schema.newValidator();
            validator.validate(xmlSource);
        } catch (SAXException e) {
            return false;
        } catch (IOException e) {
            return false;
        } catch (Exception e) {
            // Catches everything beyond: SAXException, and IOException.
            e.printStackTrace();
            return false;
        } catch (Error e) {
            // Needed this for debugging when I was having issues with my 1st set of code.
            e.printStackTrace();
            return false;
        }
        return true;
    }
}
Some Side Notes:
For creating the files, I made a simple file utility to write string to files:
public static void createFileFromString(String fileText, String fileName) {
    try {
        File file = new File(fileName);
        BufferedWriter output = new BufferedWriter(new FileWriter(file));
        output.write(fileText);
        output.close();
    } catch ( IOException e ) {
       e.printStackTrace();
    }
}
I also needed to write to an area that I had access to, so I made use of:
String path = this.getActivity().getPackageManager().getPackageInfo(getPackageName(), 0).applicationInfo.dataDir;   
A little hackish, it works. I'm sure there is a more succinct way of doing this, however I figured I'd share my success, as there weren't any good examples that I found.