Australia finished the day on 212 for seven, in some trouble after winning the toss. They only need a draw to take the series having won the first Test in Barbados.
It was an unforgettable day for 29-year-old Shillingford as, getting bounce out of the pitch, he bowled an uninterrupted spell of twenty-four overs and finished with 4-77.
He claimed the scalps of David Warner (50), Ricky Ponting (23), Michael Clarke (24) and Mike Hussey (10).
"These guys are guys who once they get in score a lot of runs. Getting these guys out is a real honour for me," said Shillingford.
"I normally get a good amount of bounce but on the second or third day. On the first day, especially with the spin I got, it was a little surprising but (when) I started getting that I started feeling well."
Shillingford could barely believe how the day had gone for him.
"I started off walking the guys onto the field. The skipper told me to keep my cool, play my normal game and from there I started feeling better and all the excitement came.
"I've never got a five-wicket haul in Test cricket. Coming up against Australia, I have a chance to get one so it's definitely something I want do, especially playing at home."
The morning session yielded just the one wicket thanks to Ravi Rampaul.
On his return to the side after a bout of dengue fever and subsequently a shoulder injury, Rampaul's second delivery came back into Ed Cowan who didn't play a shot and the ball struck him on the pad trapping him lbw.
Warner and Watson prevented any more wickets falling before lunch but were hindered by an outfield which slowed the ball down - only sixteen boundaries were hit during the day.
They put together a partnership of 83 before Watson struck a pull shot off Darren Sammy in the air to backward square-leg where Narsingh Deonarine ran in and took the catch.
The West Indies were now making far more use of the short ball. Another one from Sammy caught Warner on the helmet behind his left ear as he missed another hook shot and he had to receive some treatment.
Shillingford, operating from the Billy Doctrove End, snapped up the prized wicket of the stubborn Warner for 50.
Shillingford's delivery seemed to surprise Warner and all he could do was paddle it straight to cover where Kieran Powell took the catch.
Warner said that it had been frustrating batting on the pitch.
"In Australia it's coming onto the bat a lot easier," said Warner.
"They're running away for four, especially in Perth, it's only basically Adelaide Oval and the MCG where you really have to run for your shots.
"We've just got to work on getting our ones and twos and the boundaries aren't going to come.
"I was hitting good shots to mid-off but they weren't going anywhere off the square because it seemed a little dusty surface where the ball doesn't kick on where in Australia it skids off the square."
The bounce that Shillingford was finding caused problems for Ponting too, though he did manage to battle his way to 23 and became the second highest run scorer in Test cricket, passing Rahul Dravid's 13,288.
His joy was not to last long as he gloved a Shillingford delivery which was gleefully snapped up by Sammy.
Shillingford grabbed his third wicket in similar fashion as he found Clarke's glove and Adrian Barath had a simple catch at short-leg. Australia had slipped to 157 for five.
Shillingford had his fourth wicket when Hussey gave another gloved chance to Sammy, who dived to his left and took an excellent catch.
Ryan Harris - man of the match in the first Test - back in the side having missed the Trinidad Test, didn't last long as he missed a pull from a Kemar Roach delivery and wicketkeeper Carlton Baugh took the chance down the leg-side.
Australia were in some trouble at 169 for seven but the recalled Mitchell Starc put on an unbeaten 43 for the eighth wicket with Matthew Wade to at least take the tourists past the 200 mark.