The newer versions of Dreamweaver have a lot of goodies that the older ones didn't. Basically, all of Macromedia's products have been built to integrate with Dreamweaver. So from Dreamweaver, you can work with your Flash/Fireworks/Freehand/ColdFusion templates. So if you use any of those (or plan on using them), I would definately go with Dreamweaver.
I really can't offer any suggestions on GoLive, I've never tried it.
Hope This Helps!
Ecobb
"Alright Brain, you don't like me, and I don't like you. But lets just do this, and I can get back to killing you with beer." - Homer Simpson