If we speak of PET (aka polyester) we have to take also into account the oxygen atoms that don't contribute to heating values. The repeating unit, in this case, would be C10 H8 O5. PET is not a polyethylene-type of chemical, rather it's a xylene derivative.
PVC, on the other hand, has Chlorine, and the repeating unit is C2 H3 Cl1. Polystyrene, has as a repeating unit : C8 H8.
Polyurethane's: C10 H11 O3 N1.
Thus, as you see, the combustion calorific values may differ.
Without entering into theoretical calculations of heats of formation, I'd advise to use a simple lab bomb calorimeter with a known heat capacity, and measure its temperature increase upon combustion (by an electrical spark) of a weighed sample in excess air. The liberated energy would be the product of the calorimeter's heat capacity by its temperature rise. Divide the result by the mass of plastic used, and voila, you get its calorific value.
I hope this satisfies the query.