I did the opposite and went into a dev role right after university then later moved onto devops jobs. Getting into DevOps is relatively easy but it does require a change of mind set (some of my current colleagues came from a dev background and still refuse to fully embrace devops ways).
I think if it's a startup, it'll be easy to get into either types of roles. From my experience start ups give you massive jumps in career progression in little time even if the company barely cares about career progression. For me this has been due to the tiny size of the teams vs giant teams (my current team is 50 man, in start ups my teams have been no more than 5 people).
Having said all of that, in bigger companies there's more opportunity to pick and choose where you specifically want to focus.
I think if it's a startup, it'll be easy to get into either types of roles. From my experience start ups give you massive jumps in career progression in little time even if the company barely cares about career progression. For me this has been due to the tiny size of the teams vs giant teams (my current team is 50 man, in start ups my teams have been no more than 5 people).
Having said all of that, in bigger companies there's more opportunity to pick and choose where you specifically want to focus.
Mileage will likely vary.