Nvu is free but for the time to download it: click here
It's a pretty good program and produces clean code for the most part.
There have been one or two problems with the built in FTP publishing feature but since it is free to begin with and since the issue(s) seem to have been resolved you really can't argue with it too much.
Check out magazine covermount CDs. They often carry full version mainstream web authoring programs that are a couple of versions old. NetObjects Fusion has featured on several magazine covermount CDs and it is as good a place as any to start.
You can download a 30 day trial of Dreamweaver from the Macromedia site but I'd suggest you stay away from it for now. 30 days with a program like Dreamweaver doesn't really even allow you to scratch its surface and it isn't the simplest program to get to grips with anyway.
Try Nvu for now and browse around computer magazine cover CDs to see what you can find.