You would normally use Levenberg-Marquardt training for small and medium size networks, if you have enough memory available. If memory is a problem, then there are a variety of other fast algorithms available. For large networks you will probably want to use trainscg or trainrp.
Multilayer networks are capable of performing just about any linear or nonlinear computation, and they can approximate any reasonable function arbitrarily well. However, while the network being trained might theoretically be capable of performing correctly, backpropagation and its variations might not always find a solution. See page 12-8 of [HDB96] for a discussion of convergence to local minimum points.
The error surface of a nonlinear network is more complex than the error surface of a linear network. To understand this complexity, see the figures on pages 12-5 to 12-7 of [HDB96], which show three different error surfaces for a multilayer network. The problem is that nonlinear transfer functions in multilayer networks introduce many local minima in the error surface. As gradient descent is performed on the error surface, depending on the initial starting conditions, it is possible for the network solution to become trapped in one of these local minima. Settling in a local minimum can be good or bad depending on how close the local minimum is to the global minimum and how low an error is required. In any case, be cautioned that although a multilayer backpropagation network with enough neurons can implement just about any function, backpropagation does not always find the correct weights for the optimum solution. You might want to reinitialize the network and retrain several times to guarantee that you have the best solution.
Networks are also sensitive to the number of neurons in their hidden layers. Too few neurons can lead to underfitting. Too many neurons can contribute to overfitting, in which all training points are well fitted, but the fitting curve oscillates wildly between these points. Ways of dealing with various of these issues are discussed in Improve Neural Network Generalization and Avoid Overfitting. This topic is also discussed starting on page 11-21 of [HDB96].
For more information about the workflow with multilayer networks, see Multilayer Neural Networks and Backpropagation Training.