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A letter or other notice to the plan is not going to provide any protection unless the plan has decided that something less than a domestic relations order will suffice. The law requires a domestic relations order before a plan is required to act (including to protect a would-be alternate payee). If the plans are based in California (and maybe elsewhere) they will probably treat a California joinder order as a domestic relations order for purposes of preserving benefits until matters are resolved. A joinder is an abomination, but most plans will choke it down with the intended effect.

I am not a lawyer but the first thing I would do is send a joinder (is that the right word) notifying BOTH plans of a pending QDRO. Preferably BEFORE he files any retirement papers or make any elections with either pension plan.