Gotfrag has a large selection of demos online of (mostly) cevo-matchplay. You can learn a great deal watching those pro-players play the game.

The main advantage of watching a demo over watching a vid is the relative small download and full-screen vieuwing (as you are watching them on your own copy of tf2)

Just download a couple of the top-downloaded demo's, extract the .dem file in your C:\Program Files\Steam\steamapps\*user name*\team fortress 2\tf folder. Fire up tf2 and press shift-f2 to bring up the playbacktools and use them to select the .dem file and play it (alternatively you can type 'play *demoname*.dem in the console).

Have fun!

Yeah redrumdemos is anotehr good one with alot of 4kings matches and syre matches both of which are very good.

Cheers might have to give this a gander