You should NEVER exceed the PSI rating on the sidewall of the tire or you risk having a blowout due to increased temperature (and therefore pressure) at highway speeds.
So if mine say 28 in the front and 32 in the rear, I shouldn't load them up to 50PSI?
There are two recommended pressures - the one on your car (either inside the door on the frame of the car or in the glovebox) and the number printed on the side of the tire itself. It's okay to exceed the one on the car. The worst it's going to do is decrease tire life by wearing the middle of the tire down before the sides. It will also increase gas mileage, but when you think about the energy required to make new tires and dispose of the old ones I don't know if you break even or not.
The number printed on the sidewall of the tire should never be exceeded. That is the pressure rating of the tire. Sure, there is a lot of safety marging built into the number on the sidewall, but as the tire ages and the sidewall develops cracks that margin is going to decrease.
If you're in the market for new tires check out
low rolling resistance tires. They usually have higher rated pressures and can reduce rolling resistance by as much as two thirds. They'll have a bigger impace on your mileage if you do a lot of low speed driving where rolling resistance plays a higher factor than wind resistance.
Summary: lower than mfr's specs = faster tire wear and poor mileage (all around sucks)
mfr spec pressure = good tire wear and okay mileage
over mfr spec, but under tire rating = faster tire wear and good mileage
over tire rating = really fast tire wear, fantastic mileage, but greatly increased risk of blowout