Well, C# and VB.NET go hand in hand; if you know how to use one, you basically know how to use the other. All you need to get down is the syntax. I recommend removing your attention from any specific language and learning .NET and its concepts, rather than VB.NET or C#, since the knowledge is directly transferrable to either language. I say spend a week or so getting familiar with C#'s syntax and the few language differences it does have with VB.NET, and then concentrating on .NET as a whole.
Also, I don't know anything about the job market, sorry.