The 24-year-old from Inverurie clocked four minutes 31.76 seconds to improve on the new mark of 4:38:27 she set in the heats on Thursday morning.
England's Aimee Willmott, 21, from Middlesbrough, led for the first 350m but was overhauled in the final leg and had to settle for silver.
Keryn McMaster of Australia won bronze.
The crowd's reception for Miley when she arrived on poolside before the race was near deafening, but the swimmer appeared unaware, wearing headphones and looking at the floor.
Willmott started more strongly though, even holding off Miley in her strongest breaststroke stage before the Scot responded in the final stages with a brilliant freestyle finish.
"I tried to drown out the noise a little bit before the race," Miley, who became the first Scot to win Commonwealth swimming gold in Scotland, told BBC Sport.
"But it was really great and helped me both tonight and in the heats."
James Guy was the sixth fastest qualifier for the 400m freestyle final Further home nations medal success came in both the men's 400m freestyle and the women's 200m equivalent.
England's 18-year-old James Guy clinched bronze in the former, finishing ahead of Scottish trio Stephen Milne, Dan Wallace and Robbie Renwick.
The Scots had all qualified for the final in quicker times than their Bury-born rival but finished fifth, seventh and eighth respectively.
Despite struggling to produce a sample for doping control - meaning a two-hour wait after the morning session - Guy was able to deliver an impressive new personal best of 3:44:58 and finish behind winner Ryan Cochrane of Canada (3:43:46) and Australian David McKeon (3:44:09).
More home nations' medal success came when England's Siobhan-Marie O'Connor took silver in the women's 200m freestyle.
Australia smash world record in women's 4x100m freestyle relayThe 18-year-old from Bath only missed out on gold by 0.25 secs, with Australia's Emma McKeon taking the title in a new Games record of 1:55:57.
Her compatriot Bronte Barratt won bronze with Jazz Carlin of Wales sixth in 1:57:26.
The final event of the evening, the women's 4x100m freestyle relay, yielded another medal for England - this time a silver.
The quartet of O'Connor, Fran Halsall, Becki Turner and Amy Smith were 4.74secs adrift of the imperious Australians, who smashed the world record.
Their time of 3:30:98 was almost three-quarters of a second faster than the previous mark.
Canada took bronze and Scotland were fifth ahead of Wales, with Northern Ireland finishing eighth.
England's Siobhan-Marie O'Connor, right, took silver with Jazz Carlin of Wales, left, sixth in the medley 
Miley becomes the first Scot to win Commonwealth Games gold in a Scottish pool 
Miley retained the title she won in Delhi four years ago 
Canada's Ryan Cochrane put in a late charge to win 400m freestyle gold
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