5...b6 does create some slight weaknesses in Black's structure but after 6.Nb3 e6 Black is really not under any pressure and can continue with an eventual ..c5.
More exciting would be either 5...e5 or 5...Nd7. These moves give up b7 but Black gets good development in return. 5...e5 6.Nxb7 Qb6 7.Nc5 Bxc5 8.dxc5 Qxc5 leaves Black with a development lead and control of the center, but White has the two bishops and better structure. 5...Nd7 6.Nxb7 Qc7 7.Nc5 Nxc5 8.dxc5 e5 9.b4 a5 is a complicated position where Black is material down but White has the structural problems.
What Black should not do is defend the b7 pawn with ..Qc7/..Qc8 , that seems to lead to White advantage after Bd3.
According to other websites, although 5. Nc5 in the Classical Caro Kann variation (1. e4 c6 2. d4 d5 3. Nc3 dxe4 4. Nxe4 Bf5) is less popular than 5. Ng3, it seems to score higher.