I've used both Dreamweaver and GoLive. GoLive is much simpler, and holds your hand through the process of creation, and, with a little planning can turn out functional, clean looking sites. It is also one of the most literal WYSIWYG programs I have used, allowing you to design whole sites without seeing a single line of code. I figured it out in an evening of poking around, and its very kind to new users once you get over the initial hump of learning the interface (which in the end breaks down to drag and drop, and if you've ever used Indesign, is remarkably similar)
Its sort of the foam kickboard for web design, allowing you to jump in the deeper sections of the pool, and not sink, but it can hold you back.
Dreamweaver on the other hand would be the fins, allowing you to dive deeper into web design, but requires you to get in with the code to execute any site. This program will require a class, or at least some serious time on tutorial sites. My experience with it is limited, and I often found myself online looking for snippits of code to make the program do what I wanted. Dreamweaver also requires a much larger amount of preplanning than golive, which allows for more bumping of elements and such, as opposed to the more concrete results from dreamweaver.
Samples:
GoLive -
http://www.csupomona.edu/~pepband/Dreamweaver -
http://www.csupomona.edu/~pnehmann/firesite/