One of the best distributions for learning, in my opinion, is Slackware due to the simplicity by design and maximized usage of CLI commands. Hands down, it's a great tool to prepare yourself for more advanced distributions like B/LFS and Gentoo which require more advanced usage of CLI and low level command functions.
Coming from the fact I started on Mandrake, I can say that more automated distributions are better for general usage, while less automated ones are better for learning.
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