Depends on the car.
Although actually penetrating the engine block would likely be tricky, I'd think a square hit from a 7.62 AP round on a thin spot on the block would at least crack it and maybe even punch a hole into a cylinder wall or oil port. This could not possibly be good for an engine. They're not made of out some super-hard steel alloy, generally just cast iron or aluminum.
If you could cut the timing belt on a newer car or damage the timing chain on an older car that would shut it down right away. On newer cars a round or two into the fuel injection system or throttle body should stop it, on an older car that would be the carbuerator. On either a shot to the distributor, ignition coil, or whatever its equivalent would stop it dead. Also, if you can damage some vacuum lines you can probably shut it off. They are a particular irritation for me and have probably caused me as much swearing as any other car problem I've encountered on most cars I've worked on. But any of these things should shut down the engine and reduce the car to only moving on forward momentum.
IMO, I think you can look at it like you look at stopping a game animal or attacker. If you can make a CNS hit you'll stop it cold. Generally if a car has spark and fuel, and has them at the right time it will run. If you disrupt that you'll stop the car from running, and that's easier than actually damaging the engine's ability to turn the crank.
A shot to the radiator or water pump would also stop it, but it would take awhile before the car overheated enough to seize up.
As to making those kind of hits, I think repeated shots from anything that will penetrate the engine compartment would do that, but you'd have to know where to put your rounds. It would probably be as much a matter of luck as anything unless you knew where all the components were on every single car ever made, but more shots in more places would increase your chances.