@POTUS, according to Twitter (https://www.wsj.com/articles/twitter-says-it-is-permanently-suspending-account-of-president-trump-11610148903), is the 'official' account for the Office of the President of the United States. It is a de facto arm of the executive branch in the same way that any other public-communications aspect of the office would be. (Theoretically) When it is used, it carries the weight and authority of the Office - it is, essentially, official communication.
@JoeBiden is the account of Joseph R. Biden, a private citizen. Communication therefrom does not carry the official nature in the same way, and so to use it is ethically incorrect, if not actually illegal in any way.
The word 'republic' derives from Latin (res publica) to mean "The People's stuff." Meaning the President is acting as a trustee, responsible to the People and charged with taking care of their stuff. If the person of President and the Office of President were the same, it would be the President's stuff, not the People's stuff. It's super abstract to be sure, but it's a quintessential feature of what it means to have a republic. This was a choice made by the framers in reaction to a system where everything was understood to be owned by the monarch, divvied up among people delegated to work that land since the King couldn't do the job himself.
No firewall between trustee and beneficiary/grantor is needed under a monarchy, because they're all the same person. In a republic, however, the public are the grantor and beneficiary, and the official is the trustee - but they are also a beneficiary and grantor in part. This introduces an unavoidable conflict of interest - one that is worked around by keeping a procedural firewall between the acts of the trustee as President, and their acts as a private citizen.
Donald Trump's style as President featured a broad disregard for norms of conduct, for which he was both broadly criticized and hailed. It was entirely within his style to use his personal brand and communication channels, because he viewed himself as 'The President' instead of simply the person who was occupying the Office of the President. This is also why he got into fights with members of the White House Counsel, often claiming that they should be acting differently: He wanted them to behave as if he were their client, when in normative actuality it's the Office of the President that is their client. (There's also a string of West Wing episodes about this nuance.)
A big part of Biden's platform and entire political character revolves around re-upping political norms and restoring the traditional relationships of political institutions. To that end, using his own, private Twitter handle to broadcast official messages would be in contravention of his demonstrated beliefs and values. In fact, using it much at all while he occupies the Office could create the appearance thereof, thus why he's mostly only using it for retweets.