As I mentioned, I don't have the same setup as you (as I use a Z80 SBC of my own design), but I can give you some general comments/suggestions.
The IORQ- line won't do anything unless interrupts are enabled on the SIO and something occurs that causes the SIO to generate an interrupt. Just starting things up and initializing things will not (necessarily) cause the IORQ- line to go active (low).
On the signals that you indicate that you brought out to be able to 'scope', you don't mention WR-. I would scope the SIO CE- and WR- together, sync on CE-.
With that ready (if you have a storage scope, do a single trace) - reset/restart the system. You need to see CE- active (low) and WR- active (low) at the same time. There should be about a dozen occurences of that. That would be the start-up initializing the SIO. If you don't see that, then you'll need to track things closer to the bus. For example, does the address decode generate the CE- and does the WR- signal come through from the bus.
If you do see those writes, then it could be that the initialization doesn't enable interrupts (it uses polling), or it is only enabling them for the port you aren't sending data to. It could also be that the data coming in on the RX pin isn't being recognized as valid serial data. If the SIO isn't configured to interrupt on errors, it won't generate an interrupt unless valid data is received.
If the SIO does get the CE- and WR- signals (indicating that it is probably getting initialized), I would think that you would see something on one of the TX lines (TXA or TXB), as most boot-ups will try to print something. If you can see signals on either of those, then (with the scope) you can try to figure out what communication parameters it is using (baud, data bits, etc.).
I'm sorry that I can't be more specific. Hopefully the folks that actually have a setup like yours will come back from their holiday soon and help you out.
Let me know if that helps at all.
-Ed