check out Bert Stefani or 'confessions of a photographer'. He has great tips on how to get the most out of flash photography.
I work frequently with pocketwizards since upgrading from infrared like the canons ST E2. When I first started out on wireless flash it took a bit to understand.
do you get the same metering from the flash if you use a trigger and reciever? or does it not expose the subject propperly?
unless you get the latest pocket wizard, the mini and flex, its all manual to get the exposures correct. It takes a bit of understanding and practice to get right. I use pocket wizard plus II, they are very reliable and work a fair distance.
for pocket wizards and most transceivers and receivers you need one for the camera sitting ontop and one for each flash attached by cord.
For shooting wireless flash set the shutter to maybe 1/160th
-shutter contols the ambient light but is the only setting not to affect the flash power from 30sec-1/2000th.
Then place the flash where you think would suit. working with the setting below should help you get the correct exposure but all have factors that can affect how an image can turn out. e.g aperture/DOP, ISO/noise.
-aperture and iso can control the exposure of the flash.
-moving the flash closer or turning the flash's power up controls the exposure from the flash aswell.
Google and Youtube helps with everything. A lot of info on blogs.
Heres a photo and link for example where I had to boost up the ISO for ambient light from the sunset using speedlites/strobes.