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One easy way is to enter the VIN at Carfax.com. Even without buying anything, it will tell you basic information such as engine size (but it will be in liters, so it would be either 5.0L or 5.7L which is a 305 or 350 respectively), valve arrangement, fuel system, etc.
The ratings of the motors for 1991 are as follows:
5.0L 305-cid 170hp
5.7L 350-cid 195hp
This is according to Chevrolet Police Cars by Edwin J. Sanow.
Another way is to decode the VIN yourself. The eighth digit is the engine code. For a 305 it would be 'E' and a 350 would be '7.' Ahhh, that famous number 7.
Keep in mind that unless it was originally a police, law enforcement, or fire fighting vehicle, it will be a 305 because it was against GM policy to sell 5.7L (350) caprices to civilians, because it through off its its CAFE ratings. This policy was enforced until 1994.
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