The only reason that I know of why a formula wouldn't be available to summarize on is if it didn't reference any database fields or whose value wasn't dynamic throughout sections of the report. For example, if you have a formula that returns a constant it won't be available. Or if it only references a field that is set throughout the report and returns a value based on that field, like "if {parameter}=1 then 1" would not be available either.
In general, the formula's value should not be static through the sections of the report you're summarizing over (Though the way Crystal determines this is beyond me and this doesn't seem to be a hard and fast rule)
EDIT: One other reason why a formula wouldn't be available is if you're already using a summary function in that formula. Only one level of summaries at a time!