Maybe I'm not too clear on your inquiry, but these are the facts the way I see it.
If you fly from AMS to MXP the train ticket from MXP to Milano Centrale is €10, then from Milano Centrale to Venezia Santa Lucia is €37.50 (full base price) in 2nd class. I don't recommend purchasing ahead a discounted ticket if flying in that day, because it's hard to predict if your plane will be on time and if you miss the train, the economy ticket is invalid and non refundable.
Therefore the cost of the one way ticket from MXP airport to Venice Historical Center is €47.50 per person. If you add it to the $62 (about €45) flight cost from AMS to MXP, the total cost is less than €100 per person (air + rail). The travel time from MXP to Venice, depending on wait times etc. is about 4 hrs from airport station to Venice (maybe 5 hours from landing to stepping off the train in Venice).
If you fly from AMS to VCE, the cost is (your numbers) $195 per person, or a little less than €140 per person. From VCE airport to the Venice City center is probably about 1 hr, when everything is said and done (maybe 90 min from landing). The cost varies depending on what you use (bus, taxi, water taxi), but with a bus to Piazzale Roma you'll stay under €10 per person. So flying directly to VCE will cost you about €50 more per person compared to flying to MXP then taking the train, but it will save you about 3.5 hours.
Whether the time saved is worth the additional cost, it's up to you to decide.
