Having worked in two early stage startups and at big tech early in my career, this depends entirely on your experience level and on the engineering team’s. At a big tech company you are far more likely to work with highly experienced engineers and learn from the best then at a startup. That being said, it depends completely on who they have hired before you or on your own experience level (especially if you are employee #1). My advice is to meet the engineering team and make sure that you have a good opportunity to interact with them during or after the interview process.