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Patricia Blount wonders: <<... distinction between the two words secondly and secondarily. are adverbs. not synonyms except in one specific case. adverbs, and modify the entire sentence. second in a sequence. providing useful but less-important (secondary) information.
As a general rule, the element within the compound that word that is pluralized will receive the plural-s, but it's not always that simple. Daughters-in-law follows the general rule, but cupfuls does not. See the special section on Compound Nouns and Modifiers or, better yet, a good dictionary, for additional help.