We present a novel computational photography technique for single-shot separation of diffuse/specular reflectance, as well as novel angular domain separation of layered reflectance. We present two imaging solutions for this purpose: two-way polarized light-field (TPLF) imaging and four-way polarized light-field (FPLF) imaging. TPLF imaging consists of a polarized light-field camera, which simultaneously captures two orthogonal states of polarization. A single photograph of a subject acquired with the TPLF camera under polarized illumination then enables standard separation of diffuse (depolarizing) and polarization preserving specular reflectance using light-field sampling. We further demonstrate that the acquired data also enable novel angular separation of layered reflectance including separation of specular reflectance and single scattering in the polarization preserving component, as well as separation of shallow scattering from deep scattering in the depolarizing component. FPLF imaging further generalized the functionality of TPLF imaging under uncontrolled unpolarized or partially polarized illumination such as outdoors. We apply our approach for efficient acquisition of facial reflectance including diffuse and specular normal maps and novel separation of photometric normals into layered reflectance normals for layered facial renderings. We validate our proposed single-shot layered reflectance separation under various imaging conditions and demonstrate it to be comparable to an existing multi-shot technique that relies on structured lighting while achieving separation results under a variety of illumination conditions.