Here are some simple steps I would suggest for learning VB.NET:
1. Download VS 2005 Express or 2008 Beta (Rumor has it 2008 is going to be release around Xmas, but I've heard no release date) from here:
http://msdn2.microsoft.com/en-us/express/default.aspx Alternatively, you could download SharpDevelop if you're more of an open source sorta guy, which can be found at:
http://www.icsharpcode.net/OpenSource/SD/
2. Decide what you want to do programming wise. As I see it the biggest choice is Web programming vs. Windows programming. Personally, I mostly do windows programming, so the rest of my advice is based upon that. While it is possible to do both, I suggest you pick one just to start out.
3. Create a basic HelloWorld Console app. Start looking at the GUI builder, with a press a button to print hello world in a message box type app. If you are having problems with those, look at http://99-bottles-of-beer.net/language-visual-basic-(.net)-173.html for a basic guide on some of the syntax.
4. Read up on some of the basics of an OOP language, such as the tutorial here:
http://www.codeproject.com/vb/net/OOPS_In_VBNET.asp
5. Write a program to do some specific task. For example, build a simple calculator that just adds.
6. Download the 101 VB.NET samples from here:
http://msdn2.microsoft.com/en-us/vbasic/ms789075.aspx I'm not suggesting you work with all of these, but once you know a few basics, these are great to help with specific "How-do-I?" questions. These also give you some broad topic ideas for future development.
7. Look at some open source projects and contribute to them. For example, you could work on GAmp, a very cool little media player, if I do say so myself. You can find GAmp on sourceforge at:
http://sourceforge.net/projects/gampmediaplayer *FULL DISCLOSURE: This is a plug for my own program

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