With the growing use of optical polarization in applications ranging from communications to medical diagnoses, adaptive correction of complex vectorial aberrations in optical systems has become an increasingly important area of research. However, research to date has focused primarily on phase and retardance aberrations, whereas another major source of aberration-diattenuation-remains largely unexplored. Unlike the others, diattenuation affects intensity in addition to phase and polarization, limiting the intrinsic correction capability of adaptive systems. In this work, we propose the use of optical skyrmions to probe diattenuation-aberrated systems and provide metrics that characterize the performance of vectorial adaptive optics (V-AO), with theoretical and experimental validations. Based on the probed results, we demonstrate V-AO correction under real-world aberrations for complex media imaging and analyze correction strategies to optimize measurements in aberrated polarimetric systems. This work paves the way for high-dimensional aberration correction, introduces a previously unidentified use of optical skyrmions, and provides insights that will aid the development of vectorial measurement systems.