The identification of the set of k most central nodes of a graph, or centrality maximization, is a key task in network analysis, with various applications ranging from finding communities in social and biological networks to understanding which seed nodes are important to diffuse information in a graph. As the exact computation of centrality measures does not scale to modern-sized networks, the most practical solution is to resort to rigorous, but efficiently computable, randomized approximations. In this work we present CentRA, the first algorithm based on progressive sampling to compute high-quality approximations of the set of k most central nodes. CentRA is based on a novel approach to efficiently estimate Monte Carlo Rademacher Averages, a powerful tool from statistical learning theory to compute sharp data-dependent approximation bounds. Then, we study the sample complexity of centrality maximization using the VC-dimension, a key concept from statistical learning theory. We show that the number of random samples required to compute high-quality approximations scales with finer characteristics of the graph, such as its vertex diameter, or of the centrality of interest, significantly improving looser bounds derived from standard techniques. We apply CentRA to analyze large real-world networks, showing that it significantly outperforms the state-of-the-art approximation algorithm in terms of number of samples, running times, and accuracy.