I haven't done much flash photography, but I found this article which is pretty comprehensive:
http://photonotes.org/articles/eos-flash/
From what I remember, shoot in Auto/P mode if you want the flash to be your main source of light, and any of the other modes if you want to expose as normal but use the flash as fill light.
Also as you probably know, always try to bounce the flash of a wall or reflector rather than using direct flash. A diffuser will help to soften the light if you do need to use direct flash though.





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