We did this trip earlier this year - booked before Rouge launched its dreaded service to VCE. We travelled xxx-YYZ-MXP (AC metal) & VCE-FRA-YYZ (on LH) in P class. We traveled to Turin, Florence, Rome and Venice on Trenitalia (recommended). At the time of booking K fare = $980 & P was $2200. A no-brainer, IMO.
Milan was not our 1st choice. I follow FT, and it became obvious that the best fares were to MXP. Did we pay a premium to rtn. via VCE? Perhaps. But it was sure cool to fly out of an airport you can reach via water taxi!