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.