This paper presents a methodology for accurately gauging the true plane wave shielding effectiveness of composite polymer materials via rectangular waveguides. Since the wave propagation of the waveguides is not in the form of plane wave patterns, it is necessary to post-process the S-parameters for the measured data of the waveguide lines to obtain such patterns and ascertain the effectiveness of true plane wave shielding. The authors propose two different methods to achieve this. The first applies simple renormalization of S-parameters, where reference impedance is changed from the value for the waveguide to that for free space, which ensures good accuracy of shielding effectiveness with a small degree of discontinuity across the range of frequencies. The other relies on rigorous extraction of the composite materials’ effective permittivity and permeability ascertained from rectangular waveguides; afterward, plane wave shielding effectiveness is calculated analytically and gives very high accuracy. Both procedures assume the given samples are isotropic in character. We validated the accuracy of the methodologies by conducting tests on a set of synthetic samples of 2 mm thickness with unit permittivity and variable conductivity and on a dielectric material of known permittivity (FR4 laminate). The applicability of both methods was further proven by analyzing the isotropic composite materials, a process involving the use of iron particles embedded in a dielectric matrix. The synthetic samples and an FR4 material were tested to check the accuracy of the methods. Based on numerical studies and measurements, we concluded that materials with a shielding effectiveness of up to 25 dB could be measured at a maximum amplitude error of 1 dB to 3dB to a frequency of 18 GHz, depending on the relative permittivity of the material; hence, the first method was suitable for approximation purposes. For maximal accuracy, the second method typically demonstrated an amplitude error of below 0.5 dB to the same frequency across the entire range.