Coming from a VB background and being forced to learn C# I have hit the first hurdle.
In VB i could put all the namespaces I wanted available across the entire app
For C#, the namespaces entered in the web.config will be recognized in .aspx files, but not codebehind. I don't think it will take you long to adjust (Ctrl-. will let you quickly add a namespace when you type a class name that doesn't have the namespace referenced).
This ability is only for VB.NET, the C# project does not support it :/. But, you can create a template for new source code file ( C# Wizard Templates in Visual Studio .NET , How To: Edit Visual Studio Templates ) and change default namespaces as you wish.