We discovered that overprint effect with postcript output to EPS appears to be subject to RBG (or maybe CMYK outout) colour selection for purple.
Checking the first digital print for the live run for Champs maps, the mapper noticed that overprint was not working. Yet it had been OK in test runs. After some bewilderment, two of us came to the same conclusion from different thought processes. One clue was that we had changed the purple composition for this run. So we changed it back and got the correct overprint effect.
I notice the Help does say this process isn't perfect for Postscript output so hopefully this might make it a bit mnore perfect if not previously known. As I cannot tell whether the culprit is the one of the set RGB components or one of the components of CMYK output her is a setting that worked and another that didn't. g and y seem good initial targets but I'll leave it to Finn to suss out.
This worked: r179 g26 b255 which I believe equates to c30 m90 y0 k0.
This didn't: r179 g0 b217 which I believe equates to c30 m100 y15 k0.
We also noticed that if the EPS was distilled to EPS, an valid overprint effect appeared to disappear. If this occurs, go to Adobe Reader or Acrobat Preferences | Page Display and turn on Use Overprint Preview. Haven't had time to find out whether that also ensures it prints correctly.