They are, broadly, two different families of barley. A 6-row barley has 6 rows of kernels on each ear. If you were to slice a cross-section of the ear, you would see 6 kernels. 2-row on the other hand, has only two rows of kernels, on opposite side of the ear, with the other four (two on each side) being undeveloped. 6-row tends to have more diastatic power than 2-row.