You can use one vs all approach first and consider them as 2class classification by having the decision value option in the libSVM. This is done by having the each class as positive class and rest of the class as negative for each classification.
Then compare the decision values of the results to classify the samples. Like you can assign the sample to the class which has the highest decision values. For example, sample 1 has decision value 0.54 for class 1, 0.64 for class 2, 0.43 for class 3 and 0.80 for class4, then you can classify it to class4.
You can also use probability values to classify instead of decision function values by using -b option in libSVM.
Hope this helps..
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