You can use Java Stream API since Java 8:
String string = "test.1231.asdasd.cccc.2.a.2";
Arrays.stream(string.split("\\."))                 // Split by dot
      .skip(2).limit(1)                            // Skip 2 initial parts and limit to one
      .map(i -> i.substring(0, 1))                 // Map to the first character
      .findFirst().ifPresent(System.out::println); // Get first and print if exists
However, I recommend you to stick with Regex, which is safer and a correct way to do so:
Here is the Regex you need (demo available at Regex101):
.*?\..*?\.(.).*
Don't forget to escape the special characters with double-slash \\.
String[] array = new String[3];
array[0] = "test.1231.asdasd.cccc.2.a.2";
array[1] = "aaa.1.22224.sadsada";
array[2] = "test";
Pattern p = Pattern.compile(".*?\\..*?\\.(.).*");
for (int i=0; i<array.length; i++) {
    Matcher m = p.matcher(array[i]);
    if (m.find()) {
         System.out.println(m.group(1));
    }
}
This code prints two results on each line: a, 2 and an empty lane because on the 3rd String, there is no match.