In order to improve the steering flexibility of agricultural machinery in hilly and mountainous areas, a multi-mode steering system with front wheel steering, rear wheel steering, and four-wheel steering has been developed. The hydraulic steering system based on load sensitivity principle and proportion-integration-differentiation (PID) controlling algorithm was designed, which overcomes the negative impact of external load changes on flow control accuracy. The mechanical-hydraulic-controlling coupling model established in the AMESim and the sequential quadratic combinatorial optimization algorithm (SQCOA) was adopted to obtain the optimal combination of PID parameters. The simulation results demonstrate that the parameters such as pressure, speed, displacement of hydraulic cylinders, etc. in different steering modes meet the design requirements. To examine and verify the system performance, the test platform was researched and developed for conducting steering radius and displacement measurement. The experimental data illustrated that the front and rear hydraulic cylinders have good synchronization accuracy in four-wheel steering mode, and the fast switch of steering mode can be realized. The maximum error rate of is steering radius 4.21% and 3.77%, respectively, in two-wheel steering and four-wheel steering modes. The research methods and conclusions can provide a theoretical basis and reference for the other steering system development.