The FAA requires a safety pilot if you are flying for real. You can log “actual” instrument time as a single pilot.
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Example: Flying over the ocean at night with no moon and no horizon at all. I would argue that any time you're flying and encounter a situation where you would not be able to continue without instruments is loggable as actual.
Instrument time is, as you say, when flight is conducted solely by reference to instruments. This can further be broken down into actual and simulated time. Actual time is when you are flying in cloud or visibility below VFR minimums and cannot navigate by visual references.
To legally act as PIC, a private, commercial, and airline transport pilot must have a current medical certificate and have all required endorsements, ratings, and recency of experience for the type of aircraft being flown and the flight conditions under which the flight is conducted (FAR 61.3, 61.31, 61.56, 61.57).
It may surprise you to learn that there is no requirement to keep a logbook. The FAA has no such rule. Photo by Mike Fizer. However, student pilots are required to keep a record of their training flights.
As a VFR pilot you are responsible for terrain avoidance and avoiding other aircraft. As long as the tower clears you for a straight-in approach, there is nothing to prevent you from flying the ILS. That being said, it is fairly difficult to watch for terrain and traffic while also watching the needles.
FAR 91.109 (c)(1) says that during simulated instrument conditions, a control seat must be occupied by a pilot rated for the aircraft. Put them together and the sole manipulator can log PIC time, and the safety pilot acting as PIC can also log PIC time.
So is there any way for a not yet HP/Complex endorsed Private Pilot to log PIC time in a Mooney? Yes!As long as they fly with another pilot or instructor who is qualified to act as PIC in a Mooney (including BFR, current, medical, and Complex/HP endorsements).