How to learn MFC

Whichever method you choose for writing GUI software, it's going to be hard. it doesn't sound as if you are very experienced (are you still trying to work out which language to program with?), so I would suggest learning the all the basics of C++ first, and then learning the WinAPI. It's harder than MFC, but it will help you understand MFC more. The MFC is based on the API, i.e. MFC can only do what the API can do, so the API is more powerful.

if you are using Dev-C++ then go to the Tools -> Check for Upgrades / Packages, and try to find Rad C++. Or go to radcpp.com. It's an excellent, very easy to use way of creating GUI software with only a few lines of code.
Thanks!