You can use any of the GUI's launched from NNSTART to create some sample training code. Then customize that code by setting the following data division values:
net.divideFcn = 'divideind'; % Divide data by indices (i.e. not randomly)
net.divideParam.trainInd = [... training indices you want ...];
net.divideParam.valInd = [... training indices you want ...];
net.divideParam.testInd = [... training indices you want ...];