Honestly most of the people that approach me to learn Linux, I have them follow the Gentoo Handbook to compile and configure a Linux workstation from scratch.
It is a tried and true method. If you want to be _good_ with Linux (including administration), build it: Follow the Gentoo Handbook, and restart every time something is wrong or fails.
Alternatively, if you want to be a semi-competent user you can go the path of installing a user-friendly distribution (like Ubuntu, etc.) and get various Windows-based workstreams working (Gaming, Windows-Only Software through Wine, etc.) But this is less likely to push you to the same tier.