Metal coated Hollow Glass Waveguides (HGWs) incorporating single dielectric thin films have been widely used for the low-loss transmission of infrared radiation in applications ranging from surgery to spectroscopy. While the incorporation of single dielectric film designs have traditionally been used in metal/dielectric coated HGWs, recent research has focused on the development of alternating low/high refractive index multilayer dielectric thin film stacks for further transmission loss reduction. Continuing advances in the deposition of optically functional cadmium sulfide and lead sulfide thin films in HGWs have allowed for the simultaneous increase in film quality and greater film thickness control necessary for the implication of such multilayer stack designs for enhanced reflectivity at infrared wavelengths. This study focuses on the theoretical and practical considerations in the development of such multilayer stack coated waveguides and presents novel results including film growth kinetics of multilayer stack thin film materials, IR spectroscopic analysis, and IR laser attenuation measurements. The effects of incorporating progressive alternating cadmium sulfide and lead sulfide dielectric thin films on the optical properties of next generation dielectric thin film stack coated HGWs in the near and mid infrared regions are thoroughly presented. The implications of incorporating such dielectric multilayer stack coatings based on metal sulfide thin films on the future of IR transmitting hollow waveguides for use in applications ranging from spectroscopy, to high laser power delivery are briefly discussed.