I think you are misunderstanding how the Security Chief works. Let me explain.
InspectorThe inspector automatically charges up the shields to maximum when the Inspector arrives at an outpost or after the Inspector is involved in combat at an outpost. The Inspector does not change the max amount of shield available at an outpost.
Security ChiefThe Security Chief adds 10 shield capacity to every outpost you own, plus an additional 10 to the outpost where the Security Chief is stationed. It does not instantly charge the shields.
When a security chief is hired the capacity of an outpost's shield is increased but this shield must charge up following the usual rules.
Shield Charge in GeneralIt takes 48 hours to go from no shield to max shield. If an outpost only has 10 shield capacity then this equates to 1 shield every 4.8 hours. If it has 20 shield capacity then this equates to 1 shield every 2.4 hours. As you can see, the higher the shield capacity then the faster the recharge rate.