We consider problems of estimation of structured covariance matrices, and in particular of matrices with a Toeplitz structure. We follow a geometric viewpoint that is based on some suitable notion of distance. To this end, we overview and compare several alternatives metrics and divergence measures. We advocate a specific one which represents the Wasserstein distance between the corresponding Gaussians distributions and show that it coincides with the so-called Bures/Hellinger distance between covariance matrices as well. Most importantly, besides the physically appealing interpretation, computation of the metric requires solving a linear matrix inequality (LMI). As a consequence, computations scale nicely for problems involving large covariance matrices, and linear prior constraints on the covariance structure are easy to handle. We compare this transportation/Bures/Hellinger metric with the maximum likelihood and the Burg methods as to their performance with regard to estimation of power spectra with spectral lines on a representative case study from the literature.