I don't believe there is anything special about creating a .NET class that can be used in LabVIEW since we can access just about any object. If you want a boundary, I would say it should be CLS compliate (Common Language Specification). If you build it with VB.NET or C#, you are going to be fine. If you use C++.NET, you have to be more careful since you can easily create code that isn't CLS in C++.NET.
I would recommend picking a C# Command Line project in Visual Studio to get the "Hello World" program working. Just a simple class that outputs some text to the screen. Once you have that down, you want the C# Class Library project to make stuff you can access in LabVIEW.
Why C# over VB.NET? Personal preference. I think the C# syntax is easier to learn than VB.NET, but there are a lot of VB programmers out there that would disagree. But either should do the job.
Is there something in particular that you are looking to create?