I have 'Angel' in syndication at 4 PM (Pacific time) on Sundays on the WB and 'Buffy' on local programming on the WB Sundays at 11 PM and 'Angel' on local programming on the WB Sundays at 10 PM. I also have, as most people do, 'Buffy' at 4 and 5 PM on FX and 'Angel' at 5 PM on TNT weekdays and also two eps of 'Buffy' in the mornings.
Basically, the shows air at a certain channel and time or don't air at all depending on where you live.