Setting OPTIMIZER_CAPTURE_SQL_PLAN_BASELINES to true tells the database to store plans for repeatable SQL queries. i.e. those that run more than once.
Once the database has captured a plan for a query, this forms the baseline. Future queries will use this plan (and only this plan) if OPTIMIZER_USE_SQL_PLAN_BASELINES is true.
The system level settings define the defaults for every session.
The session level settings override the system level settings for that particular session.
So it's not really a question of which is "faster". More how you want the system to behave.
Read more about this at:
https://www.oracle.com/technetwork/database/bi-datawarehousing/twp-sql-plan-mgmt-12c-1963237.pdf