VB.Net is not difficult to learn though. If you have learned or programmed VB before (VB6), you should have the foundation already. The major different of VB6 and VB.Net is VB.Net now is part of a larger system named. Visual Studio 2005. Previously VB is an individual applicatin development tool but if has been integrated into Visual Studio 2005. VB.Net is a object oriented programming language. Unlike the previous version, you may struggle a little initially when you pick up vb.net as you need to understand namespaces, objects, classes, overloading, etc. I hope this will not scare you off. As long as you have learned VB before, you should not worry. The base structure of the language such as iteration, decision making syntax ,etc remains the same.
I would suggest you to pick up the following books to kick start your learning process
1. Visual Basic for Dummies (Wiley Publishing)
2. Visual Basic 2005 Step by Step (Microsoft Press)
3. Visual Basic 2005 JumpStart (O'Reilly)
Once you have mastered some basic skills from these books, you may wish to take a look at the WROX series book from Wiley Publishing. These books are OK but not for beginners. You may sometime 'lost' somewhere if you try to use WROX series book to teach you the basic of VB.Net.
Hope this will help. If need some help during the course of learning VB.Net, do drop me an email or message. I will try to help if possible.
Start with good tutorials or with good books. Try this title:"Database programming using vb.net and sql server", by VK publishers. This books will give you the complete application development in vb.net.