As Tommy said, in 3 days you won't really have the opportunity to go anywhere other than the tourist spots.
Staying only in the historic center, the Central Market is an interesting place (the favorite destination of all food tours) and easy to reach on foot. Go there in the morning.
Still in the "market" spirit, you can also go for a walk to the Flea Market which is mostly a lot of souvenir shops but with a few second-hand dealers in the small perpendicular alleys.
The mini-neighborhood of Anafiotika can be explored for a short hour... provided you know where to enter (and exit) :))
I made this small map that can help:
https://www.google.com/maps/d/edit?mid=1ljBd_LqYpmCOpd5bVmAyMvR6P5cAbBA&usp=sharing
It also mentions the Flea Market
Crossing the National Garden there is an exit near the Panathenaic Stadium: (you can sprint there and be cheered by your friends, like an Olympic champion) : https://www.panathenaicstadium.gr/en/home/
In the post-industrial genre I also like the Gazi neighborhood, easy to reach by continuing west after Thiseio. You will find the Industrial Gas Museum right in the Technopolis park. Yes, you can also visit huge pipes in Athens!
The place is also a venue for events and concerts.
https://gasmuseum.gr/
If you go to the National Archaeological Museum, it is possible to go for a walk in Exarchia neighborhood which is just behind. It's the historically anarchic and protest neighborhood where you will find a lot of street art, music stores, book stores, and many cool bars full of young people.
There are many other interesting places little known by tourists to explore in Athens, but for you it will be for next time.