Surprised that your previous system never seemed to need defragging, tho' if you used windows' own analyzer, I've always found that it doesn't report the true status very well,(tho' I believe that it is actually licensed from Diskeeper)!
Windows has more space to play with, so it may appear that your files are more fragmented!
Personally, I always defrag after installing a large program,say 250Mb+, and after a fresh install of windows I always defrag before I install anything else!
I use Diskeeper,and let it do it's thing automatically, unless I've been moving a lot of big files around, but I've heard good things about this one too
http://www.oo-software.com/home/en/products/oodefrag/
As a way of thinking about this, or at least how I explain the principal of defragging to people whose computers I attend to, is that Windows is the boss

that chucks all the files etc. into the filing cabinet (HDD) willy nilly, and your defrag program is the secretary, who sorts and tidies it all up!