If you don't have to learn COM for a certain purpose I would strongly advise you to pass to .NET.
It doesn't really matter if you learn C# or VB. Take the one that suits you best. All .NET languages use the same framework, so you can do exactly the same things in each of them (that is not fully true for Visual C++ .NET, but only for managed C++ code. However, if you write unmanaged C++ code, that's not really .NET programming, so...). You will see in examples that they are given usually in pairs: one for C# and one for VB, and the difference is not that big.
C# has one slight advantage: it has been written especially for the .NET framework. That means that it suits best the framework. I think though that it is a very slight advantage.
So, in my opinion, you should do the following things:
1) learn OOP principles (if you are not familiar with them already). All .NET languages are OOP, including VB;
2) read about the .NET framework;
3) learn C# or VB.NET syntax, grammar etc.
4) start playing around with what you learn. Read other forum topics, look on the web etc.
I hope this helps you.