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If you want to learn a scripting language, stay away from dreamweaver. You won't learn a thing.
As for wich to go for, it all comes down to a matter of preference really. Having a VB background will make it extremely easy for you to go with ASP, so I'd suggest that first.
Don't do PHP because everybody else is doing it. ASP is just as good as PHP. That's something you can learn once your comfortable with ASP.
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