I think these two articles will give a nice overview and "how to use" for each discipline:
Overview: http://msdn.microsoft.com/msdnmag/issues/06/00/TeamSystem/
more details: http://msdn.microsoft.com/library/default.asp url=/library/en-us/dnvs05/html/witinvs05tmsys.asp
After that you can start using TFS. To learn extensibility, I suggest downloading SDK from http://msdn.microsoft.com/vstudio/extend
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