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Have you tried the prayer for prosperity? A bronze prayer of this type will give you a single piece of paper, that you can "sell" to an NPC. The next day, it the NPC will have unlocked a new tier of his inventory.
What I ended up doing in that case was saving up the Blessings of Commerce you get from doing the Prayer for Prosperity and selling them to her in one big batch.
Though I was having another problem with her, where her on-hand money was way too low, so I had to sell the blessings back and forth, basically giving her shop a boost of money by giving mine over and that seemed to work to unlock her next Tier.
Maybe you'll be able to do the same without needing to fork over money in the process, but if the blessings aren't enough, try to increase the NPC's on-hand money as well.
However if you sell him 600 coal, he'll unlock all his teirs.
Just mine coal and sell all in one go, and then buy most of his ingots and other things. With so much being traded all at once, he'll fully unlock.
P.S:
I demoed that very thing in my tutorial (shameless self-promotion)
Besides you don't really 'have' to unlock him. Buying the cauldron is not the preferrable strategy, becuase it costs too much and making the health potion is easy.