The reflection of linearly polarized light from a multilayer system of ultrathin dielectric surface films is investigated both analytically in the long-wavelength limit and numerically by the standard way of calculating the reflection characteristics for the layered medium. The second-order approximate formulas for reflection coefficients and characteristic reflection angles are derived and their accuracy is estimated. It is shown that approximate expressions obtained for reflection parameters of multilayer system in the long-wavelength limit are of immediate interest to the solution of the inverse problem for ultrathin layered surface structures. Innovative possibilities for optical diagnostics are generated by means of polarizing and principal angles. For determining the parameters of multiple surface layers an appropriate method is found by combining differential reflectance with ellipsometry.