I\'ve been using .net for quite some time, and everywhere I interview these days, I keep getting asked about my knowledge with .NET 3.0/3.5 technologies (WF, WPF, WCF etc.)<
I think the best way to learn it is to grab a book or go on a course.
And there's no magic way of "starting to use technology xxxx in my code". Once you know what a certain technology is about, see where it can fit in your architecture.