I recommend Python 2.3.5 although the latest is Python 2.3.7 for this series/release but they don't have binary package for windows (but you can get the source release)... you can download the Python 2.3.5 
http://www.python.org/ftp/python/2.3.5/Python-2.3.5.exe
 
however, you can read the changes made in 2.3.7, just in case you are doing production job 
http://python.org/download/releases/2.3.7/NEWS.txt but not that big issue....
 
 Then later on or maybe you want to start directly using PythonWin (which comes with a new IDE) rather than using IDLE (IDE from original Python 2.3.5)... PythonWin (includes a new set of modules for windows programming/networking stuff), 
SourceForge.net: Files choose the 
"pywin32-212.win32-py2.5.exe" 
 
I think that's all you need to learn about Python, before you will go learning about python GUI using 
Wxpython (which I recommend too) although I find quick and easy using 
Tkinker just don't let yourself on hurry... instead enjoy your time learning python programming...
 
I recommend 
Alex Martelli and 
Mark Lutz books... they are so active in mailing list.... they are the best authors who can deliver great teachings... at the moment, Alex seat perhaps 2/3 seats away from Guido at google's office.... you can also visit alex martelli sites and read about his blog...
 
that's all for tonight...lol a bit sleepy now..... 


