Most of the items found were under wooden foundations.
The boot, and a smoking-pipe bowl, were found among a second, smaller deposit of items at the carpark's northern section.
The excavated area was previously registered as an archaeological site, and the digging has been monitored by Underground Overground Archaeology, archaeological and heritage consultants.
Archaeologist Dr Hayden Cawte, who oversaw the excavation for the firm, was surprised by the level of preservation of the artefacts and brickwork.
"With the foundations, you don't often see that level of structural detail, and the ceramic artefacts were in great condition," he said.
"It gives more insights into how areas were occupied and how they were used in the 19th century."
The former car park had been an industrial area, home to coal sheds and a soap works in the 19th century.
And the various bluestone and brick-paved areas and a paved drainage trench showed how efforts were made to improve a reclaimed harbour area that was initially boggy.
It had been a relatively shallow excavation.
"It hints at the opportunities that are going to arise with the work that's going to be under taken on the main hospital site."