Quantum correlations represent a fundamental tool for studies ranging from basic science to quantum technologies. Different non-classical correlations have been identified and studied, as entanglement and discord. In this Paper we explore experimentally the rich geometry of polarization Bell-diagonal states. By taking advantage of the statistical method of generation, the values of entanglement and discord along different trajectories in the space of the parameters of density matrix have been measured. The effects of sudden death of entanglement and complete freeze of discord were investigated in order to detect the domains with different domination of one type of quantum correlation against to other. A geometric interpretation for each considered phenomena is addressed. The observed good agreement between experiment and theory for all investigated trajectories ensures the reliability of this method.