Nick,
Back to your original question:
if I got my multi, I know LEGALLY I would be able to log it PIC if I'm the sole manipulator of the controlls, but obviously I couldn't go up in the Navajo by myself without knowning the plane - I would die!
You are correct that you could legally log PIC time as the sole manipulator of the controls of a plane for which you are appropriately rated. 61.51 governs logging of PIC time. You are also wise to avoid flying it solo until you know the systems well. (Not to mention, it's unlkely you could get insurance without some dual time and probably a trip to FS.)
So, my question is, whenever I have my hands on the controls, would the guy in the left seat (the real pilot) be able to log it also?
There's a big difference between acting as PIC and getting to log PIC. The definition of Pilot in Command is found in FAR 1.1. Meeting that definition is how you get to ACT as PIC. That doesn't automatically allow you to LOG PIC time. 61.51(e) governs the logging of PIC time. Assuming neither of you are ATPs and that both of you are appropriately rated for the aircraft, the only way the PNF can log the time is to be (1) a flight instructor providing instruction or (2) a safety pilot (you under the hood) who is also acting as the PIC. The latter allows him to log PIC time for that portion of the flight during which you are wearing a hood. Otherwise, he cannot log any PIC time while you are the PF. BTW, it is an error to think of him as "the real pilot".
While we're on the subject, during the current period of time where you are flying and NOT appropriately rated, the other pilot, who is most definitely ACTing as PIC, canNOT LOG the time as PIC either, since he is not the sole manipulator of the controls and the conditions of flight do not require two pilots under the regs.
The only reason why I would think he would be able to is for insurance purposes.
As mentioned earlier, there's very little chance you'll be allowed by the insurance company to get your ME certificate, and then go jump in the plane and fly. However, being required to have another pilot on board by the insurance company has no bearing on 61.51(e) logging of PIC time. The "regulations under which the flight is conducted" refers only to the FARs and not any stipulations imposed by the insurance companies. I'm sure the insurance companies would like to change that, and thus gain even more control over the aviation industry, but that's another discussion....
Now is a good time to get familiar with the difference between logging and acting as PIC. MIght I suggest you take a look at Doc's FAR Pages. There's lots of great info there.
http://www.propilot.com/doc/logging2.html
FAR 1.1 "Pilot in command" means the person who: (1) Has final authority and responsibility for the operation and safety of the flight; (2) Has been designated as pilot in command before or during the flight; and (3) Holds the appropriate category, class, and type rating, if appropriate, for the conduct of the flight.
61.51(e) Logging pilot-in-command flight time.
(1) A recreational, private, or commercial pilot may log pilot-in-command time only for that flight time during which that person -
(i) Is the sole manipulator of the controls of an aircraft for which the pilot is rated; (ii) Is the sole occupant of the aircraft; or (iii) Except for a recreational pilot, is acting as pilot in command of an aircraft on which more than one pilot is required under the type certification of the aircraft or the regulations under which the flight is conducted.
Hope that helps. A Navajo is a great plane. Get your ME certificate and start logging that time!