Find a vendor in the Actor list and open the properties. I'll use Adrianne Avenicci as an example.
Select the Factions tab and double click ServicesWhiterunWarmaidens.
Select the Vendor tab. There's two things your looking at.
The first is the Merchant container. This is what they have available to sell. Any scrolls or levelled lists containing scrolls that they sell are found here. You could add scrolls to her chest but she will never sell or buy them. Why?
The second thing to look at is the Vendor Buy/Sell List and the Not Buy/Sell checkbox. The list is a form list containing keywords and determines what they will buy and sell if the Not Buy/Sell checkbox is clear, and what they won't buy and sell if the Not Buy/Sell checkbox is marked. If we added the keyword VendorItemScroll to Adrianne Avenicci's Vendor Buy/Sell List, then she would buy them from us and sell them if she had some.
If you look at general traders (like Belethor who buys and sells everything) you'll see that they have the Not Buy/Sell checkbox marked and only two entries in the linked form list (keywords VendorNoSale and VendorItemKey). This is why they buy (almost) anything.
Yeah... which does not say anything about governing by-skill-level availability of spell tomes.
I think just certain vendors get certain tomes. I've only ever gotten super high level ones from the college. Then again, I haven't played a mage long term ever, but low end vendors never get them so it's just how their vendor chest is set up I think.
Something else is at work. Farengar will sell only up to Adept destruction spells and Apprentice everything else... but will not sell the Adept destruction spells until your Destruction skill is at 40 or so.