If you come from VB.NET, then, i suppose, you just start to program in C/C++.
- The easiest way to create C/C++/Win32 GUI applications on Windows is by using Visual C++ Express 2010 (free, and probably last free C++ IDE from Microsoft, so get it now) + ResEdit
](resource editor to add simple controls in your applications - ListBox, Edit Box, ComboBox, ListView, etc).
Then come professional GUI frameworks:
1. MFC - comes only with retail versions of VC++ and is considered outdated by many.
2. Qt - very feature rich, cross-platform and free framework, but big and not easy to learn for a beginner. Though, knowing Qt will add some points in your resume, for sure.
3. WTL - light-weight free GUI framework from Microsoft. But lacks documentation and not supported.
4. Some other less popular frameworks, including WxWidgets.
Be aware, that comparing to .NET IDEs, all these frameworks (except MFC) require some effort to install and to tune it for your needs (also, not an easy for a beginner C++ programmer).