If your switches are wired as "normally closed" and wired in series between the PMXD-416's EStop and ISO_GND pins, then switches closed should present a "0" on pin 10, and any switch open should present a "1" on pin 10. See the PMXD-416 manual section 2.5.1. That is presuming there is nothing connected to the /FAULT terminal on the 416.
Start by looking at the PMDX plug-in's "real time display. This shows you the pin states ignoring any Mach4 pin mapping. Go to the Mach4 "diagnostics" menu and select the PMDX plug-in. On the plug-in dialog, click on the "real time display" button. You should see the Pin10 indicator change when you open and close any of the switches. If so, continue below. If not, then there is some issue with your switches and/or wiring. Use a volt meter to measure the voltage between EStop and ISO_GND with switches open and closed. It should go from near 0V to near 5V (or maybe 3V, I don't recall).
Once you see the indicator in the real-time display working, verify your Mach4 configuration. You should have the PMDX-416 "Pin10" mapped to Mach4's EStop input. Go to the Mach4 configuration menu and select (rats, I don't have Mach4 on this PC and I don't recall the exact name) "Config". Then go to the "Inputs" tab and scroll WAY down to EStop. If must be mapped to PMDX-SmartBOB Pin10, with "active low" NOT checked. Click on "OK" until you get to the main Mach4 screen.
Now see if the Mach4 diagnostics tab shows the EStop toggling when you open/close the switches.