Questions & Answers about Сегодня я впервые поехал на метро.
Поехал is the past tense of a perfective verb and usually means set off / went by vehicle, with focus on the start of the trip or the fact that it happened as a single completed event.
In this sentence, Сегодня я впервые поехал на метро means something like Today I went by metro for the first time.
Compare:
- ехал = was going / went by vehicle, often describing the trip in progress
- поехал = set off / went by vehicle, a single completed event
- ездил = went / used to go / made a trip there and back, often about experience or repeated trips
So поехал sounds natural here because the speaker is talking about a first-time event that happened today.