"Also, am I right in thinking that if the Cv is 0.004 at 100%, then the Cv at 50% will be 0.002?"
No.
"Pressure drop across valve can be made up as this is variable within the system, let's assume 500psi for this example.
Assuming it's pure water at 25°C with a specific gravity of 1 (because I don't want to get into all that mess)."
I don't know how you can make up a pressure drop across the valve without the missing component of velocity. If there is no movement of the water, then the pressure loss is zero. As example, assume the water is moving at 10 feet per second, or V = 10. Then the pressure drop across the valve would be Cv times velocity squared divided by (2 times the gravitational constant). So, assuming 10'/second, the loss (in feet of head) would be 0.006 feet; minimal, which suggests a good free flowing valve design.
Let's assume now that the valve is half closed, or more clearly, that the open area is 1/2 of the open area of an open valve. In this case, the valve is now materially functioning as an in-line orifice in the system. In this case, an orifice equation would be the best approach, solving for H. From memory, the equation would generally take the form of Q (flow rate, often in cubic feet per second) = C (orifice coefficient) x A (area of orifice) x the square root of [2 x g (gravitational constant) x H (the head loss you are solving for)].
So, depending on why you need to know this information, using the area of the opening and a C of, say, 0.6, you should be able to get close enough. If you can find out the area of the valve opening at different settings, I think you could determine head loss (pressure loss) pretty readily.
"I need to control the valve to maintain a constant psi/sec drop. I was going to do a simple, "if drop is too big, close valve a bit, else open valve a bit" logic. But I thought it would be nicer to try and do it properly."
If the pressure drop is too big, making the orifice bigger will reduce it; likewise, if pressure drop is too small, you would want to close the valve a bit, making the opening smaller.
If I understand you correctly, you are regulating flow to achieve a specific pressure drop across the valve.
"Yes, I know the change across the valve. I want to know, if I open the valve x%, what will the pressure be after X seconds. That way I can just open the valve to the required %, rather than guessing and inching it open. I'd rather not guess when there could be 23000psi in the system!"
If you can determine the area of the opening of the valve at different % opening, you can use the above orifice equation very easily, if you know the flow rate. The pressure change should be fairly rapid.