Man, that show's such a specific vibe, right? The whole ultra-competent student council president secretly working at a maid cafe, with that cold-exterior-but-actually-caring dynamic. For a similar feel, I'd point you straight to 'Special A'. It's got that same academic rivalry-to-romance core, with the female lead constantly trying to beat the perfect male lead at everything. The humor's a bit more slapstick, but the tension and eventual sweetness hit the same notes.
If you liked the 'secret' aspect of 'Maid Sama', maybe give 'Kimi ni Todoke' a shot, though it's softer. It's more about a girl everyone misunderstands finally connecting with someone, rather than hiding a job. But the gradual, heartfelt romance is top-tier. The pacing on that one can be a test of patience for some people, but I found it worth it.
Honestly, I've been chasing that particular blend of pride, vulnerability, and comedic situations since I finished the series. 'Wolf Girl & Black Prince' kind of tries for a similar dynamic with a more deceptive male lead, but it didn't quite land for me—the relationship felt a bit more toxic, less mutually respectful. The search continues.