While there are many things you can do with the edge bindings (not wasting key combinations / mouse-buttons for short-cuts), the standard settings of some plug-ins might be rather annoying or confusing. If you notice any seemingly random view-port changes, plug-in activations or just "stuff moving away and around wtf!?", check your activated plug-ins for edge bindings.
While many seem to switch to Compiz in the first place because of having seen the Desktop Cube, some might find the Plane more attractive, as it offers some work-flow enhancements like being able to drag windows up or down from the current Desktop to Desktop-2 / Desktop+2
Can be used to see all your Desktops at once. Also if you don't like using a window decorator, it is a good way to drag your windows around on a or between viewpoints (just put expo on a mouse button, if you got one to spare). Blends in especially good with Desktop plane, as 2x2 (/ 3x3) view-ports enable it to use to full screen without deforming them.
As quite a few auto-hiding applications don't seem to work that well with compiz, the widget plug-in comes in handy. You can set it to show all windows you defined as widgets using the same screen border / mouse-over. Resizing (maximized) windows when adding/removing a dock seems to be more painless with widget layer than with built-in auto-hide for most docks / panels (well - the ones I tried).
The magnifier comes in especially handy if you use your Desktop from a bigger Desktop (p.E. as media-centre). Using the fish eye mode with a big radius might be most effective while trying to do minor "menu / file navigation" and setting zoom in/out to <TopEdge>Button4 / 5 lets you easily zoom with mouse only without wasting a mouse button (mouse wheel @ very top of screen).
The scale Add-on lets you easily choose a window from thumbnails to switch to, to close, or to switch it to the current view-port (see utilities / scale extensions) offering an efficient window chooser if you don't have too many open at once (10 per screen work fine for me). This one might be especially useful on a mouse button, too, if you've got one to spare.
Something something looking good here.