you can ALMOST do it. very, very close.
set the sigma 500 super to manual slave, figure out the requisite flash output using f-stop = distance/GN (GN = guide number) at ISO100 and dial in the desired flash output.
at the camera, dial in Flash Exposure Compensation = -1 or -2 stops. press "flash exposure lock" (* button if not using custom function 4.1 or 4.3) -- this will discharge the modeling flash and the sigma will also fire. Wait a few seconds for sigma to recharge, then shoot the picture.
The camera will think it sees a lot of flash output from the modeling flash (it will in fact see the on-camera flash + the sigma) so it will put out a weak flash for the main exposure. That coupled with -2 stops of FEC will produce a barely noticeable flash from the camera. Effectively all your light will come from the sigma.
Usually I go the other way around, and dial in +2 FEC just to get the on-camera flash to be noticeable.
the canon 550/580 etc EX flashes can't be used as manual slaves as far as I know. a minor advantage to the sigma.
if you're using a rebel, you'll need the hack firmware. If you're using custom functions to reconfigure the * button you'll need to turn those off.
enjoy,