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When a Windows app operates with system process, it has the highest level of privilege and can access and modify any part of the system. It can also run without user interaction or intervention. This level of access can be dangerous if the app is not properly developed or if it is compromised by malicious code.

On the other hand, the PsExec tool is a command-line utility that allows administrators to execute processes on other systems, including remote systems. It operates with elevated privileges and can be used to execute commands or applications on a remote system. However, it requires user authentication and must be explicitly granted permission to access the system.

In general, a Windows app operating with system process has more privileges and can access and modify more parts of the system than the PsExec tool. However, both can be used for administrative tasks and require proper security measures to ensure the safety and integrity of the system.