As mentioned previously, you can do an analysis of variance. I don't know if there is an Enterprise Miner node that does this either, but you can use the SAS code node to run the PROC GLM.
In general it can be hard to determine "best" clusters/segments. There are multiple measures, but some of them don't compare across types of clustering methods (centroid based vs hierarchical based). Ultimately it may be worth trying all the clustering methods, and then computing your analysis on each set. If your analysis is better on one set of segments/clusters than another, then that could be one way to determine "best."
If you're looking at the results of a final modeling, then you might need to consider a holdout set so that you're not biased in determining your best clusters. Ultimately approaching the definition of "best" in this way ties the definition of best clusters to the ultimate modeling results that you're looking for.
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