If you following proper coding practices back in VB6, .Net should not come as such as shock to you. VB6 allowed you to program in VERY improper ways, which resulted in very heterogeneous codebases, since there are many different ways to do the same thing (most of them ugly). .Net cleans up the language and for the most part only retains the accepted "proper" way to do things.
So if you have been doing things the proper way in VB6, .Net is pretty straightforward. If you weren't doing things the proper way, then it will be a learning experience.