The biggest problem with belt sprays is that their manufacturers have managed to convince the public that a couple of applications of the spray is equal to a belt replacement.
A lot of it has to do with price too- many customers would much rather pay a few dollars for a mechanic-in-a-can, than fork out a much larger sum for a belt replacement, no matter how cheap the belt is.
You also raise an interesting point about the placebo effect. If everything is as it should be on an engine, in the sense that the tensioner on a serpentine belt is operating at the correct tension, all pulleys are properly aligned, and there is no damage to any pulley, the belt should last well beyond its recommended replacement mileage, regardless of how many times it had been "treated" with some miracle spray. Then again, if say, the tensioner is not keeping the belt tight, or even one pulley is misaligned, the belt will fail prematurely, again regardless of how many times it had been treated.
Gaurav said previously that the belts on his Pajero is lasting much longer since he began treating them with wd40, and while I agree that wd40 will silence an occasional squeak, repeated applications of the stuff will also build up a residue over which the belt might start to slip. Thus, the belt squeaks because it is slipping- a new application of wd40 silences the belt until it starts slipping again, more wd40, more slippage, more wd40, and so on and so forth.
In the end, it might have been better just to replace the belt when it was due for replacement, even if it just to avoid having to treat slipping belt all the time.