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I tend to lay down a solid coat of gloss varnish, first, then finish with matte to remove the unsightly shine (details that should be shiny get a coat of brush-on gloss as a final touch).
I always use sprays for general coverage and I've found that gloss spray varnishes tend to be a lot more forgiving than matte ones, so I'm less concerned with the brand I get. I've tried a handful of matte sprays and, while it's a bit pricier than many others, I'm in love with Testors Dulcote. Nothing else has given me as even and matte a finish as that stuff.
As for how to use them, they're applied like any other aerosol spray - read the directions to see what the recommended weather range for usage is, as well as the manufacturer recommended spray distance. Start with that, using some junk models or scrap material to test and adjust accordingly.
The main things to watch out for when spraying varnishes are humidity, thoroughness of mixing, and temperature (inside the can is more important that the air, honestly). Insufficient shaking of a cold can in a humid spray environment nearly guarantees a poor finish - the varnish will cloud up, resulting in what is commonly referred to as "frosting."
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