Just had this problem for the first time - started up a fresh game after installing Cottage Living. Created an engaged couple in CAS. Things went okay with them about a week in game - Sim A cheated on Sim B with a flirtatious social, but they made up and were flirting autonomously again. Friendship bar a little lower than the romance bar which was over 50%. But on the Love holiday, even though Sim A would autonomously flirt with Sim B, she would reject every romantic social from Sim B, even "compliment appearance", as well as relationship-related ones like "talk about fear of infidelity". Tried giving them a few days, getting their regular relationship bar higher again, but no luck. I tried having her go flirt with a townie she had a mild romantic relationship with, and she again rejected the interaction when the townie tried to compliment her appearance, so the issue might not be specific to the one relationship.
I tried removing Wonderful Whims (even though they had high attraction so it should have increased flirtation success) but I still had the same problem. I have MCCC, it's up to date.
Other packs I have: Eco Living, Cats & Dogs, Growing Together, Seasons.