I have no experience with USB Serial but I will try to help you anyway.
I read your post a couple of times and I think it's missing some information:
1. "2 USB devices" -> What are those devices?
2. "the last link created (...) the first link" -> What do you call a "link" in this situation?
3. "two simultaneous USB connections" -> Could you elaborate it?
4. "(eg '2nd', '3rd' for PID)" -> Are those parameters that aren't documented?
Also:
Did you look at the "USB" labelled samples? (USB Serial, USB GPS, USB Espruino, USB Arduino)
Did you search the forum for "usb serial"?
It would be useful if you could post some code you tested.