The polarization state of radar echoes from planetary bodies contains information about the scattering mechanisms present on the surface and thus the near-surface physical properties. Polarimetric radar scatter from complex surfaces, such as those observed for spacecraft-visited near-Earth asteroids (NEAs), is not well understood in terms of relating observed polarimetry to surface properties. Here we present an improved methodology for polarimetric analyses of ground-based radar observations of NEAs, extending techniques derived for larger bodies. We calculate the Stokes vector for delay-Doppler images of NEAs and use this to perform the m-chi decomposition and derive polarimetric products such as the degree of polarization, circular polarization ratio, and degree of linear polarization. We apply this methodology to radar observations of NEAs (53319) 1999 JM8, (101955) Bennu, and (33342) 1998 WT24 obtained by the Arecibo Observatory. We also perform numerical simulations of the m-chi decomposition for irregular boulders to augment the interpretation of the results for NEAs. Our analyses show that significant components of radar echoes are depolarized (random polarization) and linearly polarized. The numerical simulations confirm that depolarization is increased by single scattering from nonspherical wavelength-scale particles. Our analysis suggests that 1999 JM8 is possibly covered in regolith and that surface scatterers dominate the scattering properties of Bennu. The NEA 1998 WT24 displays diverse polarimetric properties, which we reconcile with optical and thermal observations by assuming a fine-grained regolith mantling a rugged, dense interior. In this work, we demonstrate the usefulness of radar polarimetry in characterizing the physical properties of planetary surfaces.