.NET is more than a language - it's an entire platform. Web development is also very different from other kinds of programs.
I had 20+ years of computer programming experience before I started learning .NET. I had to start at level 0 with .NET - especially when I started with ASP.NET because I had no serious web experience, aside from very simple HTML.
There's nothing wrong with starting with a beginners book, but you might be ready to learn quicker than a brand new programmer. I like Amit Kalani's blue study guide on ASP.NET (70-315) as a great way to learn from ground zero, but still cover all of the material; even some fairly advanced stuff. A lot of people don't understand the value in certification books. Think of it this way: Microsoft paid advanced people to get together and come up with an outline that covers everything a developer needs to know about ASP.NET. Then Amit came along (a man with considerable experience teaching and developing lesson plans), and he developed training material to cover every point in Microsoft's fairly detailed outline. Amit follows a pattern I like: each section is small, and followed by a step-by-step hands-on lab to demo what you just learned.
Amit's books are best for experienced programmers who are new to .NET (Wrox has some good beginners books for new programmers). Amit makes no assumptions of prior web experience.
By the way, Amit's books are for C#, but Mike Gunderloy ported those books to
VB.NET, so that's a good choice for
VB developers.
But, with the new release of ASP.NET 2.0, and the new certification program, Amit is now updating his books. His current books were written for 1.0 and 1.1, and the labs won't work with 2.0 "as is" because his step-by-step instructions cover a lot of IDE menu functions that have changed (the code itself is probably workable on 2.0).
I strongly advise you not to start with this book ("ASP.NET Website Programming") because you'll get frustrated, and it may turn you off to ASP.NET in general. This book is much smaller than Kalani's book and it cannot target a wide range of experience. The smaller the book, the tighter it has to focus on the readers' experience level. The same is true for the new second edition of this book - the target is intermediate ASP.NET developers who already know the basics of ASP.NET, who can already create a simple application, and who already have experience with SQL Server and IIS. I think of this book as being a plan to take people from being a page developer to being a site developer.