The problem of resource allocation of nonlinear networked control systems is investigated, where, unlike the well discussed case of triggering for stability, the objective is optimal triggering. An approximate dynamic programming approach is developed for solving problems with fixed final times initially and then it is extended to infinite horizon problems. Different cases including Zero-Order-Hold, Generalized Zero-Order-Hold, and stochastic networks are investigated. Afterwards, the developments are extended to the case of problems with unknown dynamics and a model-free scheme is presented for learning the (approximate) optimal solution. After detailed analyses of convergence, optimality, and stability of the results, the performance of the method is demonstrated through different numerical examples.