Characterizing the appearance of real-world surfaces is a fundamental problem in multidimensional reflectometry, computer vision and computer graphics. For many applications, appearance is sufficiently well characterized by the bidirectional reflectance distribution function (BRDF). We treat BRDF measurements as samples of points from high-dimensional non-linear non-convex manifolds. BRDF manifolds form an infinite-dimensional space, but typically the available measurements are very scarce for complicated problems such as BRDF estimation. Therefore, an efficient learning strategy is crucial when performing the measurements. In this paper, we build the foundation of a mathematical framework that allows to develop and apply new techniques within statistical design of experiments and generalized proactive learning, in order to establish more efficient sampling and measurement strategies for BRDF data manifolds.