If you are more familiar with C++/C-styled languages, I would learn C# instead (note I was a VB 3.0-6.0 developer for a good 8 years, however, I cannot stand VB.NET and use C# instead, this is a preference tho). The language of C# (or VB.Net or ANY of the .NET languages for that matter) is not so much the stumbling point, but learning how the whole .NET Framework is used. Once you have figured out the framework, any .NET language that targets the framework can do *almost* the same things (unless the language itseslf is crippled from certain features, like JScript.NET, for example is a crippled .NET language).
Note, whichever one of the primary .NET languages you tackle (VB.NET or C#), note that they have roughly the same capabilities, an app you write in C# you can find an equivalent way to write the same exact app (look/performance/etc...) 99% of the time.
