They are very different solvers and were written by the same persons (in part).
CPO is a complete solver. The routing library uses local search, and is tuned for routing models. This it is expected to be much faster on tsp/vrp/PDP problems.
Long answer:
CPO is a complete solver, but does not contain an optimized routing library.
Before CPO, there was ILOG Dispatcher which was the equivalent of the OR-Tools routing library, using local search implemented top of the of ILOG Solver.
Actually, most of the dispatcher team actually works at Google, and rewrote the CP solver, the local search, and the routing library.
Conclusion, CPO is a great solver, but not for TSP/VRP as dispatcher was killed about the same time as the launch of CPO.