You cannot use a spectrum in classifiers such as max likelihood or SVM because these algorithms require the calculation of covariance, which requires as many samples as their are bands (nb+1). If you have ROIs with enough pixels, then you can use these other algorithms.
If you plot the mean spectrum of your classes, are they distinguishable from each other? If there is a lot of overlap (for example with different vegetation types, this is common), then it is usually difficult to get a very clean classification. if there are specific regions where they are distinguishable, you might try spectral feature fitting.
http://www.harrisgeospati...lFeatureFitting.html