My advice? Try them ALL! At least the mainstream ones. Most everything else is based on one of the mainstream distros. It's all a matter of preference. I started out with RedHat and rpm dependencies drove me nuts... Found Debian a few years later and fell in love with their apt package manager.
Most distributions these days come with a live cd so that you can try them out without even having to install them on a hard drive. Some of the ones that I would recommend you start with:
Ubuntu
OpenSuse
PCLinuxOS
Fedora
Xandros
I believe all of these (except maybe Xandros... It's a commercial distro, with a stripped down free version) have live CD or DVD versions available.
Hope this helps! The thing that makes this question so hard is that Linux can be anything you WANT it to be! With very little experience, you can take just about any distribution out there and make it as windows-like as you want.
-G