There are a couple of places this can be done.
The systemd man page does not indicate that you can append to a path as you are trying to do. Also, other mechanisms might replace the path, clearing your value from system.conf anyway. Note also that if path was empty, if you try to append to path this way, you will leave the null directory in the path, which translates to "." and it is considered a security hole to have the current directory in the path, so this may be a bad idea anyway.
Since you are using systemd, you may also be using pam_env. This tool sets environment variables from /etc/environment and /etc/security/pam_env.conf and these do support variable substitution, but see the note on the security hole above.
You said you wanted to set the variable for global services. But if you wanted to set it for shells, you could add something in /etc/profile.d/ which would be effective for sh, bash, zsh, and possibly others (but not csh). Scripts placed in this directory are sourced, and path should already be set, so appending to the path there would be safe. However, this may only work for login shells.
Environment="Variable expansion is not performed inside the strings and the "$" character has no special meaning., and forDefaultEnvironment=it only says that%-specifier expansions (like%Hfor host name) are applied. But it should be easy to find out whatPATH=$PATH:/whatever/pathresults in?