In this paper, we propose an adaptive waveform polarization method for the estimation of target scattering matrix in the presence of clutter. The proposed sequential algorithm, based on the concept of sequential minimum mean square error (MSE) estimation, to determine the coefficients of the scattering matrix, guarantees the convergence and the resulting computational complexity is linear with the number of iterations. The effectiveness of the proposed method is validated through numerical results, underlining the performance improvement given by joint transmission and reception (Tx/Rx) polarization optimization for the scalar system. Also, the results show that the vector system with transmission polarization optimization provides a comparative performance as the scalar measurement system employing joint Tx/Rx polarization optimization. Less computation burden highlights the advantage of the former mode.