There are some good resources, i'm sure people will point out to you.
Are you using the XFCE version of Statler, or the Openbox version?
There are very few major differences...
First, there isnt jockey-gtk for debian/Statler, so no 'restricted device manager'.
Configs are the same for openbox, you shouldn't use any ubuntu PPA in your sources, instead debian has 'stable', 'testing' and 'unstable' repos, unstable being the newest and most buggy, stable being the oldest but rock solid. #! uses Squeeze, which is the release that is currently 'testing', but will soon turn into 'stable'. You'll want to look up how to pin apps, so that you can get some updates for certain applications via 'unstable' without having to convert the whole system (for instance), you'll also probably want to choose if you want to convert your system to stable, testing, or unstable. For some people, thye prefer the newer updates.
Now if we look specifically at your day to day use as you requested, all your application use will be about the same, though you'll get updates and fixes much quicker (with 'unstable' anywyas).
You'll be using iceweasel by default instead of firefox, but they function about the same, and inceweasel supports the same addons as firefox.
Theres less applications in statler right now by default too, btw.
But really, you should feel right at home with the openbox version of statler 
just call me...
~FSM~
