Slackware is pretty good for learning in depth about system, but Gentoo is very good for learning the most basic parts about linux, as you have to bootstrap your system yourself. I found as an everyday system that I work on Kubuntu is best, but that is because I do not want to have to learn any more on a day by day stage... I just want my systems to work and not worry about how they do everything. Slackware was a bit to hands on for every day - but it better then when I tried gentoo (once setup, any distro should be pretty good) some such as gentoo are more about setting it up for your hardware, and the way you want it, others such as ubuntu are more about just having a working system from day one, without any fiddling (hopefully).
So Gentoo is probably the one that will teach you most about linux.
Slackware will let you learn, but you start with a stable system (older, but stable), and most config is done at the command line.
Redhat (CentOS) is really about having a supported server (most commercially supported software likes (or requires) you to run Redhat).
K(Ubuntu) and SUSE are all about everything working out of the box, and (hopefully) not having to touch the command line.
Hope this helps... (there are other distros out there, but I've not played too much with others)
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