It looks like some people in the thread below have figured it out — we actually have this. You can start a chat both ways; the system will automatically recognize if this person is on Skype for Business or on Teams.
Thanks and let me know if you have any questions.
An error occurred while saving the commentAnonymous commented
This does not work. I cant message someone using SfB as it finds their Teams client even if they are not signed in. They get message saying your teammates are trying to reach you in MS Teams.
But if they start the conversation using SfB, its fine.
The engineering team is continuing to work on adding support for multiple accounts on desktop clients. We will first launch support for 1 work/school account and 1 personal account so users can enjoy Teams for work and personal side-by-side. Windows and MacOS. Support for multiple work accounts is still being worked on and will come at a later date.
You can track status via the roadmap here: https://www.microsoft.com/microsoft-365/roadmap?searchterms=68845.