The nitty gritty of the differences:
Detail Spray has a medium lubricity and a gloss enhancer. This makes it OK for removing very light dust from the surface and will leave the paint slightly more glossy than when you started. It also is an ideal clay lubricant, pad primer, and can be used to aid in the removal of polishes and waxes from the surface in the event you went to thick on the application.
Waterless has a HIGH lubricity and no gloss enhancers, meaning after use the paint is not any glossier. It is far safer for removal of light dust on the surface as it encapsulates and lubricates potential 'swirl causing' dust much better. Its too slippery to be a clay lube, doesn't work well as a pad primer, and I wouldn't attempt to use it for polish removal as it just gums up.
Also Waterless is a couple of bucks cheaper so using it whenever you can conserves your detail spray for the things its best suited for. If you were only going to have ONE of the two in your collection I'd say go with the detail spray... its more versatile... but if you do a lot of detailing having both makes things a lot easier.
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