The trapping lasers of a magneto-optical trap have been used to bring Rb atoms into well defined oriented states. Coupled to recoil-ion-momentum spectroscopy, this provided a unique MOTRIMS setup which was able to probe scattering dynamics, including the coherence features, with unprecedented resolution. The technique was applied to the low-energy charge exchange reactions Na+ + Rb(5p±1)→Na(3p,4s)+Rb+. The measurements revealed detailed features of the collisional interaction which were employed to improve the theoretical description. As such, it was possible to ascertain the validity of the intuitive models used to predict the most likely capture transitions.