It depends on which version you use...But if you use the latest version (.NET 2.0 & VS 2005), there's not that many significant differences between the two languages...They mostly differ in syntax, and the average C# developer is perfectly comfortable writing VB.NET code, and vice versa. VB.NET has some shortcuts like 'With' and 'My', but C#, being modeled after C++ and Java, is a more terse language in general (It doesn't have the cumbersome Next, Then, Loop, End If, et al).
In 2003, VB.NET lacked the intellisense support for describing methods, classes, and parameters in xml comments that C# had, but they leveled the playing field in '05.
Personally, I prefer C# syntax for these reasons:
1. Ternary operator: ?: - much better than IIF.
2. Shorter, but equally clear, syntax. Dim x as Integer as opposed to int x.
3. Multi-line comments /* comment*/
4. Multi-line strings, string escape characters, and the @ string operator.
5. Multi-line commands without having to use the line extender character '_'.
6. C# allows you to specify parameters as output parameters (keyword out), which lets you pass values in without initializing them.
VB.NET has some goodies (optional parameters, My, and With, as well as the fact that VS macros are written in VB.NET), but all in all it is intended to ease the suffering of VB6 programmers coming into .NET, not as the primary choice for people switching platforms entirely like you are.
For a syntactical comparison, See this handy VB.NET and C# comparison.
Good luck,
-SN