The emission intensity depends on the amount of light absorption by your phosphor in the composite. The factors such as the ratio of phosphor to PVP, the dispersion of phosphor, stability, and light absorption/scattering by PVP matrix need to be considered for the lower intensity of the composite.
I think it is a matter of Beer's Law. If KCaVO4;Sm is the light absorber/emitter then doping in a system naturally causes the concentration of the phosphor to decrease, resulting in decreased emission (Pure KCaVO4;Sm is 100% a doped system may only be 1% KCaVO4;Sm). You should compare the molar absorptivity instead which is an intrinsic function of the phosphor.