Well, i would suggest that you go through the documentation in MATLAB. That should be adequate. For better understanding of the algorithms involved in networks, i would recommend the book ' Introduction to neural network systems' by J.M. Zurada. If you need further help, then please post the nature of your problem. I will address it when i can.
I strongly recommend you Netlab, a Matlab toolbox for Neural Networks.
The Netlab toolbox is designed to provide the central tools necessary for the simulation of theoretically well founded neural network algorithms and related models for use in teaching, research and applications development. It is extensively used in the MSc by Research in the Mathematics of Complex Systems.
It consists of a toolbox of Matlab functions and scripts based on the approach and techniques described in Neural Networks for Pattern Recognition by Christopher M. Bishop, (Oxford University Press, 1995), but also including more recent developments in the field. The functions come with Matlab on-line help, and further explanation is available via HTML files. The software has been written by Ian Nabney and Christopher Bishop.
An accompanying text book, Netlab: Algorithms for Pattern Recognition written by Ian Nabney is published by Springer in their series Advances in Pattern Recognition.
This latter book cover all you need to master Neural Networks from a practical point of view.