There's some information on the subject at https://www.freedesktop.org/software/systemd/man/systemd.unit.html
Various settings are allowed to be specified more than once, in which
case the interpretation depends on the setting. Often, multiple
settings form a list, and setting to an empty value "resets", which
means that previous assignments are ignored. When this is allowed, it
is mentioned in the description of the setting.
However in description of PIDFile
directive at https://www.freedesktop.org/software/systemd/man/systemd.service.html there's no information on resetting this value which according to earlier quote means it can't be reset.
Later, in section Example 2. Overriding vendor settings, there's some information on removing entries from lists:
Note that for drop-in files, if one wants to remove entries from a
setting that is parsed as a list (and is not a dependency), such as
ConditionPathExists= (or e.g. ExecStart= in service units), one needs
to first clear the list before re-adding all entries except the one
that is to be removed. See below for an example.
Cited example (edited for brevity):
Original unit:
[Unit]
(...)
AssertPathExists=/srv/webserver
Drop-in file:
[Unit]
(...)
AssertPathExists=
AssertPathExists=/srv/www
Also there's following statement:
Note that dependencies (After=, etc.) cannot be reset to an empty
list, so dependencies can only be added in drop-ins. If you want to
remove dependencies, you have to override the entire unit.