The default iOS UI is nice but if I wanted to use images for buttons instead how would I do that - is it OpenGL?
You can use images for buttons using a few simple lines of code:
// code to set image for button at normal state
[myButton setImage:[UIImage imageNamed:@"buttonImage.png"]
forState: UIControlStateNormal];
You can also use Xcode to change the type to "Custom" then you can set images for each button "state."
You can read more about UIButton states here