I don't see how they could enforce it. I suppose they'd have to create a list of every website (worldwide) where a VPN could be accessed... and then try to block it.
And even then, Starlink would still be accessible.
Discussion
He will reach out to any vpn provider with a brazilian base and demand all user data. If the companies don't comply they will be subject to heavy fines and imprisonment. Based in his latest judicial rant he my try to prosecute companies outside the brazilian jurisdiction as he is trying with Elon Musk.