Ahh, I see! Thankyou muchly!
K_CityHubs.xml has this going on
<!--******************************-->
<!-- Settlement, Level 1: Outpost -->
<!--******************************-->
<ImprovementType InternalName="Outpost">
<!-- Item Shop - Base Items -->
<UnlocksShopItem>SaltedPork</UnlocksShopItem>
<UnlocksShopItem>GnarledClub</UnlocksShopItem>
<UnlocksShopItem>Staff</UnlocksShopItem>
<UnlocksShopItem>TravelingBoots</UnlocksShopItem>
<UnlocksShopItem>Recruiting_Shirt</UnlocksShopItem>
So, out of all pre-reqless items, only those will appear. Anything else needs either to be assigned pre-reqs, or have a similar line added to an improvement. So given I don't want to be fiddling with existing buildings, I'm best off just not trying to make items without pre-reqs.
It's a bit weird that the padded set (apart from two bits that do have pre-reqs) doesn't appear in the shop. Maybe that should be something to look at.
Right now, there's really no way for the item itself to identify which shops it will show up in, but I'll add it to the modding ToDo list!
I hope you can make that change, as it would be much cleaner for modding to be able to just set it up within the item itself, rather than also having to tamper with other files.