The visitors were 51-2 at tea on day two at the Melbourne Cricket Ground, still 423 runs adrift after the hosts were all out soon after lunch on the back of Smith's dogged 140.
Yashasvi Jaiswal was not out 23, weathering a fiery blast from Australia's pace attack, with KL Rahul bowled by Cummins for 24 on the cusp of the break.
Skipper Rohit reverted to his usual role as opener after dropping to six in the past two Tests.
But it did nothing to help his woeful recent form and he was out for three, spooning an attempted pull shot off the Australian captain to Boland at mid-on for a simple catch.
The hosts resumed on 311-6 after a dominant opening day where all their top four blasted 50 or more to lay a solid platform.
That thrilling action was also notable for Virat Kohli's shoulder barge on debutant Sam Konstas, with the Indian superstar fined 20 percent of his match fee.
Australia plundered another 163 runs on Friday, with the composed Smith slamming 13 fours and three sixes.
Paceman Jasprit Bumrah took 4-99 and spinner Ravindra Jadeja 3-78.
Smith padded up again on 68, with Cummins alongside him on eight.
They took 15 off one Akash Deep over before Smith hooked Bumrah for six to rub salt in the wounds, with India's body language showing their frustration.
Smith reached his 34th Test century with a boundary off Nitish Kumar Reddy, which came on the back of a return to form in the last Test in Brisbane where he made 101.
It was a patient innings from the 35-year-old and moved him alongside four other players on the all-time list of century-makers, including Sunil Gavaskar and Brian Lara.
Only six men have scored more, led by Sachin Tendulkar's 51.
With the landmark out of the way, both men began swinging the bat and Cummins paid the price, caught for a fine 49 by Reddy in the deep off Jadeja to end a 112-run stand.
Starc was bowled by Jadeja for 15 in the first over after lunch, with Smith following in bizarre fashion.
Facing Deep, he danced down the wicket looking to drive but got an inside edge, with the ball bouncing off his pads and trickling onto leg stump.
Nathan Lyon (13) was the final wicket to fall, lbw to Bumrah.
The five-match series is locked at 1-1 after India won by 295 runs in Perth before being crushed by 10 wickets in Adelaide. The rain-affected third Test in Brisbane was drawn.
