Let's start with Dwarves.
Medic/Bookworm/Beancounter
Unfortunately game does assign initial expedition leadership somewhat randomly, and he didn't get it. This will result in mild annoyance when discussing import/export deals, but we can live with that.
Miner
Straight no-nonsense. He will improve skill fast, while digging. Skill level influences speed of excavations and amount of stone left behind. I sometimes start miner with no skill when expecting to dig a lot of sand and not pressed for time or stone. But here we will want to feed the Stonecrafter early and with as much as possible.
Money-spinner ( Stonecrafter )
Preference for crossbow bolts and balista parts pretty much sold the name
Also no-nonsense, skill level as high as possible to cut down on low quality merchandise, no hobbies.
Mr DIY
Absolute minimum in all of above. Most of this stuff just has to be done with quality not being a concern and if we want him to engrave, smoothing floors is a quick and sure way to train the skill.
Food Processing Guy
We are not going to sell food or booze, at least initially, so it's enough for him just to know the basics. Actually I should have probably given him no skills whatsoever, but meh, 6 more turtles won't save us.
Farm Girl
Da Boss
Both made the same way. Planting skill directly influences chance of getting multiple crops from one seed, we want to hit that stage ASAP. Herbalism is for gathering plants in early spring while our farms are being dug. This will not be relevant as far as feeding us goes, but will ultimately provide us with a cache of surface seeds to plant, thus enhancing variety of booze in our stocks. Thus they don't really need to be efficient at it.