<>as long as your writing .NET Managed Code. the language doesn't matter. coz the result of all the languages will be the MSIL. so it really doesn't matter which language you are using.
VB.NET is for those guys who are VB6 developers. so that ppl don't face any such problems in Migration.
C# is for those guys who are Java and C++ Developers but are looking for some ease of use.
and as far as job is concerened i am a hobbyist... so i dont care about job.
well i started .NET with VB.NET to learn the basics and fundamentals of .NET Framework (how webservices/gc/xml/ado.net works) then i started learning the C# and now i am comfortable with both the languages.