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First off, I'd read up about highlander. http://steamcommunity.com/sharedfiles/filedetails/?id=163882605 should go over some of the basics, though if you're going to go into UGC (more for North Americans than ETF2L, which is European) some bits of it will be different (weapon bans, how to sign up).
I don't know what class you main / intend to play as, but from there I'd go look up guides and tips for your class (in the guides section of steam, on google, or on youtube). If you get a 6s guide, those work too, since the general playstyle for any 6s classes (other than pocket) will be the same in highlander.
From there: http://www.ugcleague.net/forum/forumdisplay.php?77-Iron
or
http://tf2center.com/
Just know that tf2center can be pretty hit-or-miss. While it's pretty common to have an extremely helpful player guide you through the basics and help mentor you, you've got about an equal chance to get someone be toxic get mad at you for being new. Tf2's competitive scene is a lot nicer than most games', but it still has its share of toxic players.