Gaussian covariance graph model is a popular model in revealing underlying dependency structures among random variables. A Bayesian approach to the estimation of covariance structures uses priors that force zeros on some off-diagonal entries of covariance matrices and put a positive definite constraint on matrices. In this paper, we consider a spike and slab prior on off-diagonal entries, which uses a mixture of point-mass and normal distribution. The point-mass naturally introduces sparsity to covariance structures so that the resulting posterior from this prior renders covariance structure learning. Under this prior, we calculate posterior model probabilities of covariance structures using Laplace approximation. We show that the error due to Laplace approximation becomes asymptotically marginal at some rate depending on the posterior convergence rate of covariance matrix under the Frobenius norm. With the approximated posterior model probabilities, we propose a new framework for estimating a covariance structure. Since the Laplace approximation is done around the mode of conditional posterior of covariance matrix, which cannot be obtained in the closed form, we propose a block coordinate descent algorithm to find the mode and show that the covariance matrix can be estimated using this algorithm once the structure is chosen. Through a simulation study based on five numerical models, we show that the proposed method outperforms graphical lasso and sample covariance matrix in terms of root mean squared error, max norm, spectral norm, specificity, and sensitivity. Also, the advantage of the proposed method is demonstrated in terms of accuracy compared to our competitors when it is applied to linear discriminant analysis (LDA) classification to breast cancer diagnostic dataset.