Based on Jay Walker's answer above, this is a complete working example that adds the ability to do the indexing:
<configuration>
    <configSections>
        <section name="registerCompanies" 
                 type="My.MyConfigSection, My.Assembly" />
    </configSections>
    <registerCompanies>
        <add name="Tata Motors" code="Tata"/>
        <add name="Honda Motors" code="Honda"/>
    </registerCompanies>
</configuration>
Here is the sample code to implement a custom config section with collapsed collection
using System.Configuration;
using System.Linq;
namespace My
{
   public class MyConfigSection : ConfigurationSection
   {
      [ConfigurationProperty("", IsRequired = true, IsDefaultCollection = true)]
      public MyConfigInstanceCollection Instances
      {
         get { return (MyConfigInstanceCollection)this[""]; }
         set { this[""] = value; }
      }
   }
   public class MyConfigInstanceCollection : ConfigurationElementCollection
   {
      protected override ConfigurationElement CreateNewElement()
      {
         return new MyConfigInstanceElement();
      }
      protected override object GetElementKey(ConfigurationElement element)
      {
         //set to whatever Element Property you want to use for a key
         return ((MyConfigInstanceElement)element).Name;
      }
      public new MyConfigInstanceElement this[string elementName]
      {
         get
         {
            return this.OfType<MyConfigInstanceElement>().FirstOrDefault(item => item.Name == elementName);
         }
      }
   }
   public class MyConfigInstanceElement : ConfigurationElement
   {
      //Make sure to set IsKey=true for property exposed as the GetElementKey above
      [ConfigurationProperty("name", IsKey = true, IsRequired = true)]
      public string Name
      {
         get { return (string)base["name"]; }
         set { base["name"] = value; }
      }
      [ConfigurationProperty("code", IsRequired = true)]
      public string Code
      {
         get { return (string)base["code"]; }
         set { base["code"] = value; }
      }
   }
}
Here is an example of how to access the configuration information from code.
MyConfigSection config = 
   ConfigurationManager.GetSection("registerCompanies") as MyConfigSection;
Console.WriteLine(config.Instances["Honda Motors"].Code);
foreach (MyConfigInstanceElement e in config.Instances)
{
   Console.WriteLine("Name: {0}, Code: {1}", e.Name, e.Code);
}