Degenerate four-wave mixing (DFWM) spectroscopy is shown to provide a facile means for probing angular momentum (or rotational) anisotropy in nonequilibrated ensembles of gaseous molecules, with judicious selection of experimental conditions permitting quantitative determination of population distributions and Zeeman coherences for magnetic sublevels of the target species. A theoretical description of the nonlinear response induced under such circumstances is obtained by incorporating a state multipole expansion of the zero-order density operator into a perturbative (weak-field) treatment for the DFWM interaction. Aside from allowing the effects of incident field polarizations and phase-matching geometries to be considered in detail, this compact spherical tensor formalism provides guidelines for the extraction of spatial information from rovibronically resolved spectral data. Furthermore, these analyses have identified unusual polarization schemes that lead to signal generation only in the presence of rotational anisotropy, thereby suggesting a new class of four-wave mixing measurements that permit the selective detection of molecular orientation and alignment.