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Considering it for my Gorebeast Chariot and Chaos Knights to speed up painting them.

Also, would it be better to prime them black, and then do the spray, or just the spray alone?

I use the heck out of GW's Leadbelcher spray with Nuln Oil and Necron Compound for quick metal parts, especially in bulk. On assembled vehicle kits I'd probably undercoat white and brush on Leadbelcher... it covers well, and I've had trouble covering it with other colors.

The spray certainly gets you a nice hard surface finish. Some of my washes just bead on the surface...

I've used Army Painter's Plate Mail Metal and Gunmetal sprays for a while. Most of the time, they're fine. occasionally, the finish is a little too glossy and washes bead up - in that case, a quick dust of matt varnish will sort you out.

I've done everything from an Astral Claws army in Epic and 40k scale up to the chassis of Imperial Knights and a Warhound titan using those colours.

I have an opinion on GW's Leadbelcher spray, but it's not a particularly good one. It has a noticeably lighter tone than what you get in the normal Leadbelcher pot and it isn't as metallic and shiny. Depending on what you want to do, this may get in the way of things.

That said, if you use it the same way I do, you're not likely to run into trouble. I bought my can to speed things up on terrain pieces. Not that it saves me putting on a base layered of brushed on paint, but I can be a lot less neat with it. If I miss a spot, the primer will cover it up. That's dependent on putting a wash on the base layer, which I do by default. After two layers of washes, a different silver tone is irrelevant. It sort of speeds things up for me, but honestly it's not very noticeable and doesn't give me much of an advantage over black primer.

As far as your idea is concerned, going off of that I'm not sure it would speed up painting a chariot. Whether you have to paint up the non-metal bits after a silver primer or the metal bits after a black primer by hand probably won't make a difference. Not so much that I would buy a can specifically for that. If you have one on hand, though, a full coat of black with a selective coating of silver could be worthwhile.

I use leadbelcher spray for my necrons. While it gives a great rounded coverage I find it doesn't take paint over the top of it very well. It seems to make the surface a little too smooth. It's fine for necrons as there's not a lot else to paint over, not sure if I'd go ahead on something that will take considerably more work post spraying.

I suppose you could invest jn some liquid mask. Undercoat black, mask up the bits you dont want to be silver then spray away. Would help with spme of the issues that people report with overpainting.

I'm not a fan of either. They go on well enough, but it's hard to get a smooth, even finish on small parts.

Vallejo has a line called Metal Color, I encourage you to take a look at those. Very good through an airbrush or out of the container.

I used Army Painter Gunmetal spray on my Knight chassis, and I was pretty happy with the results.