Plasmon waveguide resonance (PWR) Raman spectroscopy provides chemical content information with interface or thin film selectivity. Near the plasmon waveguide interface, large increases in the interfacial optical energy density are generated at incident angles where plasmon waveguide resonances are excited. When a polymer of sufficient thickness is deposited on a gold film, the interface acts as a plasmon waveguide and large enhancements in the Raman signal can be achieved. This paper presents calculations to show how polymer thickness and excitation wavelength are predicted to influence PWR Raman spectroscopy measurements. The results show the optical energy density (OED) integrated over the entire polymer film using 785 nm excitation are 1.7× (400 nm film), 2.17× (500 nm film), 2.48× (600 nm film), 3.08× (700 nm film) and 3.62× (800 nm film) higher compared to a 300 nm film. Accounting for the integrated OED and frequency to the fourth power dependence of the Raman scatter, a 532 nm excitation wavelength is predicted to generate the largest PWR Raman signal at the polymer waveguide interface. This work develops a foundation for chemical measurements of numerous devices, such as solar energy capturing devices that utilize conducting metals coated with thin polymer films.