I've been there. I used to have a job where I wrote code, did all the infrastructure stuff, wore the DBA hat, did user support, fixed the electric stapler when it jammed, and whatever else came up that might be remotely associated with IT. It was great! I learned a little about everything.
As far as the care and feeding of your database box, I'd recommend that you do the following:
Perform regular full backups.
Perform regular transaction log backups.
Monitor your backup jobs. There's a bunch of utilities out on the market that are relatively cheap that can automate this for you. In a small shop you're often too busy
to remember to check on them daily.
Test your backups. Do a drill. Restore an old copy of your most important databases. Prove to yourself that your backups are working and that you know how to
restore them properly. You'd be suprised how many people only think about this during their first real disaster.
Store backups off-site. With all the online backup providers out there today, there's not much excuse for not having an offsite backup.
Limit sa access to your boxes.
If your database platform supports it, use only role based security. Resist the temptation to have one-off user specific security.
The basic idea here is that if you restrict who has access to the box, you'll have fewer problems. Secondly, if your backups are solid, there are few things that come up that you won't be able to deal with effectively.