This analysis explores the theory and design of dielectric multilayer reflection-enhancing thin film stacks based on high and low refractive index alternating layers of cadmium sulfide (CdS) and lead sulfide (PbS) on silver (Ag)-coated hollow glass waveguides (HGWs) for low loss transmission at midinfrared wavelengths. The fundamentals for determining propagation losses in such multilayer thin-film-coated Ag hollow waveguides is thoroughly discussed, and forms the basis for further theoretical analysis presented in this study. The effects on propagation loss resulting from several key parameters of these multilayer thin film stacks is further explored in order to bridge the gap between results predicted through calculation under ideal conditions and deviations from such ideal models that often arise in practice. In particular, the effects on loss due to the number of dielectric thin film layers deposited, deviation from ideal individual layer thicknesses, and surface roughness related scattering losses are presented and thoroughly investigated. Through such extensive theoretical analysis the level of understanding of the underlying loss mechanisms of multilayer thin-film Ag-coated HGWs is greatly advanced, considerably increasing the potential practical development of next-generation ultralow-loss mid-IR Ag/multilayer dielectric-coated HGWs.