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The blessings deck is indeed mainly a countdown. Occasionally, certain cards care what card is the top card of the blessings deck discard pile, such as Blessing of the Gods, or lycanthrope monsters. However, you never play the cards from the blessings deck, or acquire them.
When a card lists several skills in the check to acquire, you need to make one of these checks, and you can choose which one you try. You can only try one of them, though. If you do not have a skill, you can still try a check, but you use a d4 then.