We present a polarimetric analysis of the four-wave mixing (FWM) signal emitted by thick tissues, in order to extract structural information on molecular order and orientation. A careful analysis of the polarization distortions introduced by the birefringence of the sample is conducted for the proper interpretation of the results. FWM, compared to other well-known nonlinear optical methods such as second-harmonic generation, gives access to additional information on the symmetry of the molecular distribution. Furthermore, it brings the advantage of being generated in any kind of sample, even when centrosymmetry is present. The model developed here is applied to thick rat-tail tendon samples, composed essentially of collagen fibers. We show that, once the birefringence of the sample is completely characterized, it is possible to retrieve the even-order components of the molecular orientational distribution up to the fourth order of symmetry.