A popoff valve is just a simple pressure valve that goes between the turbo and intake. It's just set at a certain PSI based on the spring. Any pressure above that, from overboost or backpressure or whatever, will be vented out.
A BOV actually hooks to your intake, and opens when there is a pressure difference between the engine and turbo sides of the throttle body.
And yes, your main form of boost control should be the wastegate. This allows exhaust gas to exit, which keeps the turbo spinning in its optimal range. With just a popoff valve, you'd be letting the turbo spin way up (generating lots of extra heat in the process) then venting the extra boost. It's good as a safety item, but not as the sole means of boost control.