Personally, I haven't used neither, but why don't you take a look at The GUI Loft? It's supposed to be pretty good as a quick design tool for Win32::GUI, which will let you experiment all you want to see if it suits your needs without getting your hands dirty.

If your code isn't supposed to be portable, Win32::GUI will most likely give you the most Windows-like looks, and it's the best way to go IMHO. Otherwise, I think you should reconsider using something like Perl/Tk, Glade-Perl or wxPerl...

Good luck!