During jump-starting, we connect the boosting battery to ground rather than to the dead battery's - terminal for the simple reason that this provides a more direct return path to the good battery which is powering the dead car: the return current does not have to travel through the dead battery's minus terminal hookup cable and then to the jumper cable, but can go directly from the chassis ground to the jumper cable.
A more direct return path allows for better current flow and less voltage drop, like plugging a big appliance directly into an outlet, rather than via an extension cord.
In case you're also wondering why the plus jumper connections are made first, then the minuses. This is because there is no harm done if you leave the minus jumper dangling in the chassis of the car. Anything it accidentally touches is likely to be ground. If you connect both alligator clips on one end before connecting the other end, the other end is now live and you can accidentally touch the clips together to create a short circuit. If you connect the minuses/grounds first and then go to connect one of the pluses, you can create a short circuit, because the opposite side plus is probably dangling and touching something that is grounded.
