It's tough to do this without creating the potential for conflicts with other mods, but hey, that's what merged patches are for.
The way I've been doing it, each vendor has a respawning container hidden somewhere in the wasteland. The container is full of Leveled Items, each of which is basically a list of objects - armors, weapons, misc. items, etc. You should make your own Leveled Item listing the things you want to add (be sure to select the "Use All" checkbox, or only a few of the items in the list will be included at random). You can then add your leveled item either to the container, or to a leveled item that is in that container. It depends on which vendors you want to carry your items.
To find the right containers and leveled items, you can backtrack by selecting the container form type, and filtering for your merchant's name (figuring out the right name can be a little tricky). Also, some of the leveled lists that show up are used by multiple vendors - for example, VendorChestGeneralStore (I think that's what its called) is used by Moira, Seagrave, Karl, Wolfgang, Tulip, and possibly others. If you add your list to that leveled item, it will show up in all of those vendor's inventories.
One more thing to note, if you look at the AI data (I think) tab for the NPC vendor in question, they'll have different merchandise types enabled under autocalculated services. Make sure the equipment type that you're trying to add is selected. If you have to select it, it could create a conflict with NPC overhaul mods like Project Beauty, so you might want to avoid this if possible by using a different vendor.