Simply put, the 4 points of a phillips screwdriver are tapered - narrow at the tip, then progressively wider toward the back of the tip.
Posidriv, aside from them having an extra 'rise' between the 4 points, have 4 points that are not tapered, the ribs of the 4 points are the same width from the front of the tip to the back of the tip.
It's possible to use a phillips head driver on a posi screw. However, it'll have a tendency to cam out, or lose grip, on the screw head as you turn the screwdriver. If it's a #2 posi screw, a #1 phillips might work better if it's not too tight.
But, a posi tip on a phillips head doesn't work very well, it cams out much easier because the non tapered, wider blades on the 4 tips doesn't mesh into a phillips screw. Again, a smaller tip might work if it's not too tight.
I have a set of Wera (German brand) screwdrivers and posi drivers that have laser tipped ends, so I can get away with using either most of the time. The lateral laser lines give the phillips tip more gripping power.
As far as spraying a stuck bolt or screw with penetrant, I have a lot of experience with this. I've used every brand under the sun, and WD40 is probably one of the weakest of the bunch when dealing with seriously frozen threads (which, obviously, is common on grills). The best I've found is Kroil. It has loosened screws that no other penetrant could. Spray it on and give it 20 mins. If still no joy, spray it again, come back in an hour, give it another shot, then wait another 20 minutes. It'll come loose. I've already sprayed and waited overnight on some parts. If overnight, it comes apart like it was never stuck to begin with.
EDIT - I'm not saying Kroil has loosened every stuck bolt/screw I've worked with. Some don't come out.
Then it's a matter of doing it old skool - cutting off the head and drilling it out. A (good, not China made) set of extractors and reverse drill bits will get it done too, but that's the no fun, last resort option.