Well, database constraints are here to ensure your data are stored in a consistent manner. Form validation might have different rules depending on the functionnal context. Imho it is not a good idea to rely on database constraints to validate forms (I use the Symfony validator component for that).
From a purely technical point of view, if you want to use the database as validation layer, the hardest part is to extract why data could not be inserted / updated. Even if you could get this information from the Exception message, this will validate fields one by one until all fields are ok.
If you still want to go with it, catch the Pomm\Exception
thrown and get the SQL error code from it.
Hope it helps.