14d) Organise a smart crew first for cavalier (3-2-4) M?N T? ?R??
21d) Religious ceremony broadcast correctly (5) R????
24a) Freezing conditions for a kick-off in new La Liga (7) ??A?I??
27a) Concept that Hugo devised hasn't advanced (7)
Best thanks in advance for your help.
I would suggest MAN at arms (singular) as cavalier is singular.
If you crew a boat you MAN it plus anagram of A SMART(at arms).
Just my interpretation!!