It's best to start with a more basic language, so you can learn syntax, basic string manipulation and variable handling. Once you have the basics, then you can move up to say VB.NET.
Once you know the basics, you can branch up into any other languages, but some are more difficult than others.
If you insist on learning say .NET right off, then VB.NET is probably the best choice.
But Python is a great one to cut your teeth on.
Rich