The method you're looking for is charAt. Here's an example:

String text = "foo";
char charAtZero = text.charAt(0);
System.out.println(charAtZero); // Prints f

For more information, see the Java documentation on String.charAt. If you want another simple tutorial, this one or this one.

If you don't want the result as a char data type, but rather as a string, you would use the Character.toString method:

String text = "foo";
String letter = Character.toString(text.charAt(0));
System.out.println(letter); // Prints f

If you want more information on the Character class and the toString method, I pulled my info from the documentation on Character.toString.