Say that Player X is 2nd in the initiative. 1st is the Black Court vampire that is in a rage and taking a swing at Player X. Player X gets a built in defense [Athletics/Fists + 4dF] but can Player X instead use his action this turn to cast his Rote Evocation Shield?
It is not his turn in the initiative order. A Block is an Action that a Player can take on his turn.
Thematically though, it seems to make sense that the char could cast a Rote Evocation Shield in response to an attack ahead of him in the initiative order. At least thematically in the books. Also, the example in YS252, shows him reacting to an attack by Agatha Hagglethorn by bring up his shield.
I am hoping there is some as yet undiscovered dark corner where this concept is covered or squashed.