I started with Slackware, and that's what I'd recommend if you really want to learn Linux (which is fun, and a great resume booster!). First, it's more of a barebones distribution so it will run faster on an older computer. Second, if you install RedHat/Fedora, Mandrake, etc. it's quite possible that you'll never actually learn Linux. They come with so many point-and-click config and administration tools that you could easily use it and never have to see a bash shell, manually edit config files, download and compile tarballs, recompile your kernel, etc. It'd basically be like Windows but without as many applications and games. Slackware has very little in the way of configuration tools, package management, etc., so it forces you to learn your way around Linux.
That said, I use Red Hat/Fedora these days. It's very widely used/supported, and the package management/autoconfig tools do come in handy when I have 5 servers that I need to deploy right away and then administer. And since I use one distro consistently, I can hop on any of the several servers I deal with and know exactly where everything is (various distributions tend to put configuration files and such in slightly different places, which can get annoying). So it's convenient, but when I need to compile a bunch of custom software or solve a weird problem, I'm very glad I have the experience I got from cutting my teeth on Slackware.
Oh and I don't know how Debian is these days, but the last time I messed with it (5 years ago or so) it was sheer hell. I don't think I ever got the setup boot up successfully. I'm sure it's better now, but after that experience I haven't been too willing to spend more time with it.
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