I would say, start with asp.net and move on to MVC. Visit asp.net
] site, which has lot of help full resources.
Here is another good link to start learning asp.net: http://asp.net-tutorials.com/
Also, Google for asp.net tutorials and you will find lot of resources.
You can start on WCF, WPF later when you feel comfortable with asp.net.
All the Best.