As paypal states you can have 2 accounts then is it possible to send payments from premier over to personal?
I am confused about why you are asking this. You can send payments to any kind of accounts. If you are looking for a way to avoid fees, any payment sent to personal must be cash account payments and they will not get fees.
Yes you can do it coz it doesn't breach any PP TOS. But why you do this? Why not directly cash out the money at premier account?
Do it only if you want to breach your contractual agreement with paypal. https://www.paypal.com/us/cgi-bin/webscr?cmd=xpt/UserAgreement/ua/USUA-outside#receive-policy