What is the best way to have calls answered by a live person vs going right to queue?

Matt - you could try the following for the first scenario:

Have inbound calls ring the receptionist DID directly.  Using the Skype for Business client, sign in as the receptionist and configure unanswered calls to forwarded to the PSTN number of the Call Queue or AA.   The default setting is 20 seconds but you could choose a shorter or longer duration. 

Configure your AA or Call Queue to handle the call appropriately.

BTW - This will still work if you are using VVX phones.  The setting made in the Skype client will be honoured by the phone.  (you just can't access that setting via the VVX) 

As for your second scenario, there is nothing available today that can handle this.  I suspect/hope that will change in the near future.  What you could do as a work around is simply have a few phones that are signed in as the receptionist.  Its not very elegant but might be suitable in the short term.