Quote Originally Posted by C02 View Post
...Coming from a web design background, I value having as much control as possible over my application design as possible - I don't care about things like how fast I might be able to complete an entire application - libraries like Qt, therefore, are out of the question for me.
How can you even make that determination based on your level of knowledge?

To underscore my point
Quote Originally Posted by C02 View Post
Will Win32 API give me the control I want or would I need to step into other areas, for example Visual C++?
Visual C++ is not a language, you don't step into it, it is an IDE (tool set) provided by Microsoft.

Any sane programmer would not use pure WIn32 for almost any kind of GUI programming on Windows unless you like poking yourself with the sharp stick into an eye.
As was mentioned, MFC is a choice, QT also works, free wxWidgets and of course you also might consider using .NET (C#) for all your GUI needs.