I think we need to keep in mind what these two different liquids do, and what is in them.
Setting agents are for reducing the surface tension of the water. They are more commonly known as wetting agents. If the water wets the painted surface better, the decal will be in more complete contact with the surface. The most common wetting agent is acetic acid. If you have ever done photo darkroom work you remember the stuff. Dilute soap/detergent solutions are also wetting agents. Acetic acid is the main constituent of vinegar. If you want to cut costs by using vinegar, be sure to use white vinegar. Other types of vinegar have other constituents, including sometimes a fine powder which is not good on your model
Decal solvents, however, soften the decal so it conforms to bumps and curves better. However, as a solvent, overuse can destroy a decal. Also, after you apply the solvent the decal will be very soft, so you must touch it with true tender car- best if you don't touch it at all. Decal solvents usually contain any of various organic solvents.