Mutualistic networks in nature are widespread and play a key role in generating the diversity of life on Earth. They constitute an interdisciplinary field where physicists, biologists and computer scientists work together. Plant-pollinator mutualisms in particular form complex networks of interdependence between often hundreds of species. Understanding the architecture of these networks is of paramount importance for assessing the robustness of the corresponding communities to global change and management strategies. Advances in this problem are currently limited mainly due to the lack of methodological tools to deal with the intrinsic complexity of mutualisms, as well as the scarcity and incompleteness of available empirical data. One way to uncover the structure underlying complex networks is to employ information theoretical statistical inference methods, such as the expectation maximization (EM) algorithm. In particular, such an approach can be used to cluster the nodes of a network based on the similarity of their node neighborhoods. Here, we show how to connect network theory with the classical ecological niche theory for mutualistic plant-pollinator webs by using the EM algorithm. We apply EM to classify the nodes of an extensive collection of mutualistic plant-pollinator networks according to their connection similarity. We find that EM recovers largely the same clustering of the species as an alternative recently proposed method based on resource overlap, where one considers each party as a consuming resource for the other party (plants providing food to animals, while animals assist the reproduction of plants). Furthermore, using the EM algorithm, we can obtain a sequence of successfully-refined classifications that enables us to identify the fine-structure of the ecological network and understand better the niche distribution both for plants and animals. This is an example of how information theoretical methods help to systematize and unify work in ecology.