Site security is comprised of many parts. As a hosted service, the security of the server is out of your control. You will only be able to affect user connections to the database and coding practices to prevent sql injection attacks...
Adding users with limited abilities is certainly useful, though I find that PHPMyAdmin is not the best tool for the job. Grants on tables have a lot of options and the tool simply doesn't cover them all.
What those grants are is a application dependant, in ours, where I am tightening up security (currently all users have root access to the db (yeah I know, but I just started here and the security issue was never looked at when they started on the app)) where I created three users based on the roles those users play in the application...
some have select only
some have select, update and insert
a few have select update, insert, delete and create table privs
The other main thing to look at is sql injection, if a user puts some sql into a text box and it executes what are the results...
a common one is
username : bob
for pass word you type in: ' or 1=1
//your standard sql statement is
select userid, name from users where name='$username' and pass='$password'";
//this translates to...
select userid, name from users where name='bob'and pass='' or 1=1'";
//this gives automatic access because although the password name is technically an empty string ( '' ), the value 1=1 always evaluates to true and therefore the 'user' is granted access
You should cover all aspects of security where you have control. The code needs to validate all user inputs and the connections should limit the scope of what that user can do. Here is an article that looks at this from an ASP perspective, but its the same for php as the sql is just a relevant.
hth