What to look for, what to look for???
Four tires, two keys, one engine. Good to go!
Test drive the car - take it on uneven pavement to figure out if it needs an alignment. Take it up to highway speeds and cruise at 2,500RPM or so, to see if there is an exhaust drone in the cabin (common - it's some sort of harmonic which you either live with or change the exhaust to correct). You say that you want to daily the car, so these things might affect your commute and make it more liveable.
At 50,000Mi, the car is on it's 2nd or 3rd set of rear tires and probably it's second set of fronts. If not, expect to change them. Air con is supposed to be run monthly to lubricate the system - check that it works. At 3-5,000 miles, there should be some life in all the tires. If it's a 2016 or 17 with that mileage, have the battery tested.
LE's had the Parrot radio. I think they had a radio. It should have all of the updates to make it somewhat more useful than it otherwise is. It's purpose is to fill a hole in the dash. If you want something more, expect to put a better head unit in. There are people who want a nice radio in their 4C. The rest of us really don't use it. Your call. As a daily, I assume you will want a reliable bluetooth feature and maybe some apps (Waze), which does not describe the Parrot. The Alpine that came later is not much better. If you care.
Get the key for the stupid storage pouch between the seats. It is worthless, but if you buy one from Alfa you need to leave your left nut with them in exchange. Also, be sure to get the removal key for the radio, as I suspect you may want to remove it.
The car should come with a funnel kit and compressor / tire slime.
Otherwise, note that the paint typically sucks - so expect swirls. With 50 miles, maybe not, but if someone looked at the car from across the room, there will be resulting paint imperfections. Consider a paint correction (if required) and as much paint protection film as you can afford.
Welcome to the forum, and good luck!