Hi Rob! I might be able to shine some light on it. Here's what I would do.
If you're using a swordsman armor for example. There will likely be a corresponding material to go with it, which you can search via the asset editor. Inside the .mtl file will be a list of the textures attached to it. You'll want the diffuse texture, so if you head into the pantry and find the .dds file for it, grab a copy of it and put it somewhere so you can play with it.
Open the dds file in Photoshop. It'll probably be a weird colour because dds files are BGR, not RGB (or something like that) so just add an adjustment layer - channel mixer I think it's called - and in the blue channel, set red to +100 and blue to 0, and then in the red channel do the opposite. This should now show you the colours you see in game.
From there you can add a new layer and paint anything you like (or even create a tint map for your model if you wish, but I'll go into that bit after). When you're happy with your changes, just save the dds file and name it something unique.
In ModBuddy's Asset Editor you can create a new texture file, so do that and import the dds you just saved. Next, you'll probably want to create a material (or you can just copy the original asset's .mtl file from the pantry in the same way you copied the texture). With the material file open in ModBuddy, change the diffuse texture to the new texture you just created. If you've created a new material, you'll want to stub out the other textures as Deliverator mentioned in his tutorial.
Once you've done that, you can change the model's .ast file to point to your new material, and voila! You have a custom texture and material attached to your asset.
Disclaimer: I apologise if I've missed a step, am writing this from memory. If I have, someone please correct me.
Almost forgot! Tint maps! If you paint 100% white over the parts of your model you'd like to recolour in ModBuddy with via the tint variations in the units.artdef I believe, then just save the dds with the white parts you've created on a black background and repeat the same process above. Instead of adding it to diffuse, you just want to add the new tintmap texture into the tint field instead of the diffuse. This will allow you to create multiple variations of your asset quickly.
Anyway, I hope that helps!