With any project that is important - i.e. something for broadcast or a important client I would export a Master in a high quality format - ProresHQ (standard Prores also pretty good), AVC-Intra100 or DNx120. The last two (for me) are specific broadcast requirements for certain deliveries.
If it was a quick, less important project - might go straight to H.264 export - if an H,264 is all that is required.
Say something for social media.
One of the main reasons I export first to the high quality format is ...
all my premiere pro projects are set up to reflect the required output.
For example, if my deliverable is DNx120 - the sequence settings and preview rendering settings for that project are also DNx120.
So when we go to export - any previously rendered parts in the sequence will export very quickly and do not need to be rerendered again for export. Once we have the export - that goes back into Media Encoder to export any other versions. Be that H.264 or any other codec. Plus we have a high quality master for archiving and future use.
You also ask "will there be any quality differences when exporting H.264 straight off the timeline instead of from the ProRes digital master"
Effectively no*.
* actually yes - but nothing likely percievable by eye. Assuming you are using Prores or ProresHQ.
Prores LT has a lower datrate and you might start to see some VERY slight visual differences between the H,264 direct from your timeline and the H.264 encoded for the Prores LT file. This is called 'concatenation' and is the result of encoding between different codecs