Let me preclude this with my post may be only specific to the market area that I live in.
I do agree with Brian that C# probably will not be the fastest track to productivity for you, given your background
VB.NET does make sense to learn at the outset and get your feet wet with .NET. However, I would suggest learning C# sooner rather then later (if in fact programming is what you do for a living and not a hobby) as, at least in my general locale, C# developers are favored much more then their
VB counterparts.
The transition from Desktop Apps to ASP.NET should not be to terribly difficult for you since you have experience with ASP, things will be done differently for sure, but most of the same concepts will apply.
In so far as Books are concerned, it depends on how much a new comer you are but here are some suggestions:
Wrox's Visual Basic 2005 Express Edition Starter Kit (ISBN:0764595733) is geared towards first time programmers and uses VBExpress 2005 throughout the book.
Beginning Visual Basic 2005 (ISBN:0764574019) - This has a little of everything that you spoke about in your original post, XML, ADO.NET, etc so it might be a particularly good book for you.
hth.
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Read this if you want to know how to get a correct reply for your question:
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Technical Editor for:
Professional Search Engine Optimization with ASP.NET
Professional IIS 7 and ASP.NET Integrated Programming
Wrox Blox: Introduction to Google Gears
Wrox Blox: Create Amazing Custom User Interfaces with WPF and .NET 3.0
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