You can use both 'first' and 'firstly' to begin a list of reasons or arguments or to say in the first place/ before anything else or to list how things happenend or how they will happen. 'Firstly/ first, this car looks awful and secondly/ second, it's unreliable.
Most people think that If you begin with 'firstly', you should continue with 'secondly' and if you begin with 'first' you should continue with 'second' and not mix them up.
'Firstly' has become less common and some think it is more formal.