>So, I am now looking at the choices and am wondering which way to go. Do I learn VB.NET, or C#, or ADO.NET, or all of them?

Well, ADO.NET is just a feature of the Framework that both C# and VB.NET use.

As far as learning one over the other, no matter which one you start off with, chances are you'll be able to figure out the other one automatically.

Question, what looks more natural to you:

IF .. THEN
END IF

or

IF {
}

If the first one, start off focusing on VB.NET, otherwise, try C#.

THe only other thing to keep in mind is the language personality. VB.NET will continue to pave its own path in the RAD department, while C# while do more to target the Java/C++ crowd.

Personally, I'm more fond of C#, but thats just me.