Would you be so kind and explain exactly why you prefer this program?
I think you're on the right track though. Get a basic knowledge of HTML and CSS first. Then, pick up either Dreamweaver or GoLive - whichever interface you prefer. From there, you can eventually become more comfortable with HTML and CSS to where picking up the other editor is fairly easy. Once you're familiar with GoLive or Dreamweaver, you at least know what kind of features and tools to look for, they're just usually in a different place.
Dynamic sites can be a deciding factor though. Dreamweaver offers tools for working with dynamic sites (for instance, PHP and a MySQL database) to where you wouldn't have to write the actual code. If you need a quick dynamic solution, Dreamweaver might be the way to go, and more and more sites require some kind of database + server script solution these days. For me, I'm already familiar with PHP and MySQL, so I just write all my own code and GoLive suits me just fine.
Also, if you think you'll be looking for employment or planning to work with a team of other web designers, there are a lot more people using Dreamweaver than GoLive.
To keep myself from being overly dependent on a certain editor, I try to avoid proprietary features in any of them when possible and I usually force myself to use more than one tool. For instance, I work on most of my sites in GoLive. But I keep a handful in Dreamweaver and even do some entirely with BBEdit just to force myself to use the source code.