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Van in question: 2002 e-150 conversation.

Due to financial constraints I am only doing window insulation on my van this fall. My plan is to use rtech EPS foam board and reflectix. Right now I just have blackout curtains.

I do not want to be obnoxious and have obvious reflectix in the windows but I also want to have the proper air gap for it to be useful and to best utilize it's UV reflecting properties.

My thought it to go:

Window / curtain / reflectix / air/ foam / interior.

Is this an ideal order?
No airgap for windows, you aren't insulating with the Reflectix, you are bouncing the incoming radiant right back out the glass before it has the chance to heat up air or anything else.

The backing foam is your insulation against conducted heat coming in the glass, you could add an air gap between the foil and the foam, but more foam would be easier and better.
Might be helpful for those on a budget:

Also, on my window van with 5% tint, having the reflective surface on the other side actually makes it harder to see.
You can't tell that there is a gap and a mylar backed panel. The little bit of light just bounces back out at the viewer.

Also, you don't need an air gap between a radiant barrier and insulation (foam in your case).
The insulation IS the air gap the radiant barrier needs to function properly. That's what insulation is. Trapped air.

Lastly, keep in mind that you can bounce out a lot of the radiant energy by using high quality tint and/or reflective tint.
I tried just using reflective material but my tint isn't dark enough. How much will having some blackout fabric between the window and the mylar affect the insulations effectiveness of reflecting heat?

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Radiant energy is not the same as heat.
It passes through materials and is absorbed or reflected at different rates depending on those materials.
You will gain more heat from the dark material absorbing light than from it absorbing radiant heat.
My suggestion is just using a darkish fleece material available from Walmart for cheap.
I've done reflectix, foam with fleece, foam with fleece over 80% tint, and black paint plus foam. The only thing I was happy with was painting the windows black from the inside then cutting foam panels to fit. It looked like super dark tint and seemed better at keeping heat out. It was also the cheapest solution. Everything else looked like reflectix or fleece and would trap moisture on the window.

I'd only use reflectix if I wanted to be able to cover and uncover the windows often, since it is durable and flexible. It's really just expensive bubble wrap.

I used latex paint, but I've heard plasti-dip is easier to peel off later should you choose to do so.
I love how my windows turned out. There's a pretty light tint from the factory in my windows and what I did is sewed some reflectix inside two pieces of white fleece cloth from walmart in the shape of my window frame. I got sew on Velcro and sewed all the way around and got the adhesive stuff for the window frames. Sure maybe reflectix wasn't necessary since it was shielded by the fabric anyway but I wouldn't change a thing about them after living with them for a year. The temperature difference is staggering. If there's a cool morning and I have the covered windows facing the sunrise the fabric won't even get warm until around noon.

White reflects the most light, which is nice, but believe it or not the white fabric looks REALLY unassuming in the windows. For some reason it doesn't stick out at all. I know what you mean about reflectix looking obnoxious. It's funny when I'm driving down the road and I see a 200k RV with some crinkly reflectix stuffed in a window. It's so ugly. If I remember I'll post a picture of my window covers from the outside I think you'll like them. They're pretty cheap and if I can can make them anyone can.
Mirror window tint is the best option for reflecting heat but isn't always legal in some areas.
It reflects heat right at the glass minimizing radiant heat.

As you noted, dark window tint is needed to hide reflectix effectively in a stealth situation.

Has anyone tried professional vehicle wrap vinyl?
I'm talking about the kinds used to cover vehicles in promotional artwork.
They can be in custom colors and applied to windows.
If you found a color that matched your vehicle closely might be the perfect stealth way to block light and not look too out of place.