I began quite a while ago now with redhat 5.2 followed closely by debian 2.1. I believe this was around 1998, and I have had a distro of some sort installed since then. To name a few distros I've tried, in no particular order; mandrake, suse, progeny, caldera, lindows, Linux from scratch, gentoo, arch, Ubuntu (and numerous spins), mint LMDE, fedora, redhat, centos, various BSDs, Slackware, slax, salix, sidux, puppy, damn small, vector, crux, knoppix... I am forgetting many many installs here. The point is I seem to have gone through periods of learning a lot about some of these, and some I formatted and never turned back in less then 15 mins (caldera and lindows, I'm looking your way). I spent a lot of time in Slackware with windowmaker, on a pentium 266, when my main machine (at the time an Athlon 900) was out of service, loved it. Have always had a distaste for RPM based distros and have stayed clear for the most part, with occasional check-ins to see what has progressed. Gentoo was always my favorite (technical distro), even with the 3day - 1 week install process compiling the entire distro from scratch pulling in the entire install over dial-up. But I always come back to debian, and usually sway between debian testing, and unstable.
Very often the difference between the distros is just the desktop environment.
I have to disagree with this. The difference between distros is much more than skin deep. Since as you say, changing desktops is usually only a command or two away. From my experience some of the biggest differences between distros, is package management, and the way startup scripts are handled. Once you start to (or as used to be the case, had to) configure things by hand, and delve into the system below the desktop, you very quickly realise just how differently some distros handle things. That's the beauty of playing with, and seeing which distro you like. It's why we all become comfortable with, and favour different distros.