This doesn't make sense. There is no way to manufacture a ball with a core of one material and a shell of another material. The geometric center of the ball loses reference during the spherical grinding process, and there is no way to keep the center of mass aligned with the geometric center. You would end up with an imbalanced ball, or a statistical spread of imbalanced balls around a few lucky ones. If you hand-picked perfect ones than the yield would be less than 5% and the cost would be astronomical.
The only way to manufacture a balanced ball is to use a homogeneous material, or keep the density integral of all parts of the ball exactly the same.
The glossy "shell" or "glaze" that you see on high quality balls is not a different material, but just the vitrification of the resin into an amorphous layer using heat. The cost of the ball is less dependent on the resin used, and more dependent on the amount of heat energy needed to cure the balls, which can take up to a week in the oven at different temperature stages, etc, and offsetting electric/natural gas/oil bill costs for the factory.
Polyester is a thermoplastic (not a thermoset) and doesn't require baking to cure. It is a cheaper process but inferior because it melts at temperatures seen by contact points of skidding pool balls on cloth. Thermosets don't melt since they are completely crosslinked in three dimensions.
It is very possible that salesmen of these products don't understand their product fully.