According to reports, he also used foul and abusive language courtside to pregnant British captain Anna Keovathong - whose room number he'd asked for at the press conference.
He was reported to have described the British duo as "f***ing bitches" during a rant on court.
Nastase had also been riled by the umpire appealing to the crowd for calm with the Romanian captain interjecting: "It's not the opera, what's your f***ing problem?" After a lengthy delay to proceedings, Nastase was banished to the stands before being finally kicked out of the tournament.
Now Shriver has come forward as another victim of disrespectful and creepy conduct by the former World No. 1 and two-time grand slam singles champion.
Shriver burst onto the professional tennis circuit as a 16-year-old when she made a run through to the final of the US Open in 1978, losing to champion Chris Evert.
She went on to win 22 grand slam doubles titles and became a darling of Australian tennis after marrying Aussie actor George Lazenby and becoming a tennis commentator with Channel 7.
Shriver and Lazenby divorced in 2008.
Shriver said Nastase regularly asked her if she was a virgin until she had to order him to back off after four years of questions.
"In my first two years on the tour, I recall right when I was around my final US Open at 16, when I saw Ilie Nastase for the next four to five years, anytime I saw him at any tournament he would ask me the same question," Shriver told BBC 5live Radio.
"It was 'Are you still a virgin?' I'm a teenager, I'm playing the tour and it was a shocking thing. I'd never had anybody ask me that before.
"He was a known jokester and he did it in a joking way but I can remember as I got older - I was about 20 and it must have been the 30th time he asked me that same question - I just said, 'Would you please stop, would you stop asking me that'.
"Sort of to his credit, he never asked me again. I set a firm boundary and he stopped."
Shriver said she believes Nastase's career as a tennis official is over after the International Tennis Federation (ITF) suspended him following his antics during the Fed Cup tie.
"You want the punishment to match the crime and he behaved really badly," Shriver said.
"I think it has all gone too far. I think it is over now, I think he is done as a coach, certainly in any formal setting.
"Everybody has a couple of different sides to their personality and certainly not all of Ilie Nastase is evil and mean and sexist. But unfortunately he does not have a filter and there is a side that is, so he can't coach women players any more."
Nastase was suspended on Sunday for his foul-mouthed and abusive behaviour during Romania's scandal-hit Fed Cup tie with Britain.
In another bizarre twist, British captain Keovathong revealed Nastase had sent her flowers in a peace-making gesture.
It is too little too late for many tennis commentators for Nastase to save his career.
The ITF also released a statement when it announced Nastase had been suspended pending an investigation.
"The ITF's Internal Adjudication Panel has issued Ilie Nastase with a provisional suspension under the Fed Cup regulations for a breach of the Fed Cup welfare policy at the tie in Constanta," the ITF said in a statement.
"Nastase may not participate in the Fed Cup in any capacity with immediate effect and shall be denied access to, and accreditation for, any ITF event including Fed Cup."
However, Nastase blatantly ignored the ban on Sunday and turned up at the venue on the Black Sea coast, walking into the VIP lounge before being asked to leave by the Romanian Tennis Federation president.
After his slur against Williams, who will give birth in September, Nastase was still raging on Sunday (AEDT).
He was warned twice by the umpire for unsportsmanlike conduct as Konta took on Sorana Cirstea in the day's second rubber.
Nastase screamed at the umpire: "It's not the opera, what's your fucking problem?" Konta broke down in tears after the abuse - leading to the rubber being temporarily suspended - and left the court, subsequently being criticised by her opponent Cirstea for overreacting.
"With all due respect to Sorana she was not in my shoes on that end of the court being verbally threatened," Konta, beaten by Simona Halep on Sunday, told the BBC.
"Any abuse is not alright, but when it's a couple of metres away from you, screaming at you, I think that's a different ball game."
Amidst the controversy, Romania won the tie when Irina-Camelia Begu beat Heather Watson to qualify for the World Group in 2018 while Britain were relegated to the Europe/Africa Zone.
