When I finally got my iron mine operational, my priorities were:
Wrought & Steel for BW
Hammer and Anvil
Metal Plow - The difference in the time it takes my farmers is huge
Pickaxes - Mining, Cellar digging, stone harvesting
Shovel - Clay Digging, stump removal
Metal Saw - Great for when board Q is of no matter (housing, barrels, buckets, etc)
Scythe - A nicety for the farmers, but not always used due to the reduction in cargo capacity
Haven't even bothered with weapons or armor yet, as at our level, unarmed and leather is more then enough for what we're capable of.