I think you might want to start with the Unity documentation:
[GUI Basics Tutorial][1]
[GUI.Button reference][2]
I'm sorry for only providing links, but I think writing code for you or extensively explaining how the GUI system works wouldn't really help you. (also since there already **are** good tutorials)
[1]: http://docs.unity3d.com/Manual/gui-Basics.html
[2]: http://docs.unity3d.com/ScriptReference/GUI.Button.html
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