We present a new methodology based on directional data clustering to represent white matter fiber orientations in magnetic resonance analyses for high angular resolution diffusion imaging. A probabilistic methodology is proposed for estimating intravoxel principal fiber directions, based on clustering directional data arising from orientation distribution function (ODF) profiles. ODF reconstructions are used to estimate intravoxel fiber directions using mixtures of von Mises-Fisher distributions. The method focuses on clustering data on the unit sphere, where complexity arises from representing ODF profiles as directional data. The proposed method is validated on synthetic simulations, as well as on a real data experiment. Based on experiments, we show that by clustering profile data using mixtures of von Mises-Fisher distributions it is possible to estimate multiple fiber configurations in a more robust manner than currently used approaches, without recourse to regularization or sharpening procedures. The method holds promise to support robust tractographic methodologies and to build realistic models of white matter tracts in the human brain.