I finally switched from Chakra to Arch a few weeks ago and I thought it was going to be this giant post, but it was a lot easier than I thought. The only problem I had was that I tried to install xorg myself without following the beginner's guide. Other than that, I got KDE set up, installed other window managers, etc. Everything has been fantastic, though I did have a few problems with sound and time sync, everything's been worked out so far.
I absolutely love being able to have both KDE and GNOME apps. Don't get me wrong, I still love KDE to death, but only having a select few in Chakra really made me feel limited. I've also gone ahead and installed a bunch of other Window Managers like Fluxbox, Openbox, Enlightenment, and even GNOME3. And what's more amazing still, I've actually be switching in between them decently regularly. I spent a few days in GNOME3, then rebooted into Openbox, and now I'm back in KDE.
Anyway, yeah, it was surprisingly easy, but still so much fun. You've just got to stick to the beginner guide, even if it's just giving you the correct package names to install.