Dreamweaver isn't the problem. It's the languages it supports. If you know HTML, Dreamweaver just makes your job easier. If you know CSS, Dreamweaver just makes your job easier. If you know... Dreamweaver is not a program like say Excel or Photoshop or others where it's actually doing a lot of work for you. Dreamweaver just makes it much easier and faster to create web page code. It's a shortcut, and a good one at that.
Now if you want to take full advantage of Dreamweaver, there's a lot to learn, but it's not too bad... assuming you know some HTML, CSS, etc. If you don't know HTML, etc. then it can be a bit of a pain. Let me try to come up with an analogy...
Imagine there is a program that will create a fantasy baseball lineup for you based on certain parameters you set for the team. If you understand baseball and have some idea of players and what's important, then the program will likely be fairly easy to use. However, if you've never heard of baseball before and don't know anything about the game, then the program is likely going to be a pain in the butt to use.
Make sense? Sort of?
At worst, go through the tutorials under the Help menu. Macromedia actually does a good job with their tutorials and they're worth checking out. Again though, if you don't understand the first thing about HTML, it could be rough going at first.