if you are in windows, the easiest way to GUI programming in Python is to use .NET forms. use the free SharpDevelop ide (clone of Visual Studio). the documentation on .NET forms are plenty.
if for some reason you dont fancy .NET forms and wishes to use cross platform GUI libraries, I suggest you use wxPython. you will learn to use most of the widgets by looking at the wxPython demo application. if you want to have full documentation, use the wxWidgets documentation. the documentation for wxWidgets and wxPython are the same and it will indicate if there are differences. wxWidgets is the core gui library being shared by wx derived libs like (wxPython,wxPerl,etc)
the time will come when you get fed up hardcoding your wxPython based GUI driven apps. for that you will need a WYSIWYG ide, i suggest you use the cross platform wxDesigner ide.