Half of the ministry are women and there are more working parents in the shadow executive than ever before.
"All of us have a child aged six or under," Mr Shorten told reporters in Canberra on Friday.
Ms Plibersek replaces Labor's former foreign affairs spokesperson in government, Senator Bob Carr.
Ms Plibersek, who as deputy was able to choose her portfolio, said she picked foreign affairs because it was "an area I've had a long interest in".
"I was particularly interested in the international development part of the foreign affairs portfolio," she said.
News that makes sense
Your trusted source for staying up-to-date with the world around you. Get free daily news updates and analysis, straight to your inbox.
"And the Centenary of Anzac, again, is something that I've had a particular interest in."
As expected, Chris Bowen becomes shadow treasurer.
But Penny Wong has given up her previous portfolio to Tony Burke, who becomes shadow minister for finance.
Senator Wong now takes responsibility for trade and investment, against the government's Andrew Robb.
Mr Shorten also said his team represented generational change within federal Labor.
"There is more Gen X in this shadow line-up than has existed before in Australian politics," he said.
"But this is balanced ... with both experience in government and in opposition."
Labor's new defence spokesman is Stephen Conroy, who was previously communications minister under former prime minister Julia Gillard.
Senator Conroy will be assisted by MP David Feeney.
Mr Shorten's challenger for the leadership, Anthony Albanese, will oversee infrastructure and transport, as well as tourism.
SHADOW CABINET FULL LIST
Bill Shorten - Leader of the Opposition
Tanya Plibersek - Deputy Leader of the Opposition, opposition spokeswoman for Foreign Affairs and International Development
Penny Wong - Leader of the Opposition in the Senate, opposition spokeswoman for Trade and Investment
Stephen Conroy - Deputy Leader in the Senate, opposition spokesman for Defence
Anthony Albanese - opposition spokesman for Infrastructure and Transport, opposition spokesman for Tourism
Chris Bowen - shadow treasurer
Tony Burke - opposition spokesman for Finance, manager of opposition business in the House
Mark Butler - opposition spokesman for Environment, Climate Change and Water
Kim Carr - opposition spokesman for Higher Education, Research, Innovation nd Industry; opposition spokesman assisting the leader for science
Jason Clare - opposition spokesman for immigration
Mark Dreyfus - shadow Attorney-General, opposition spokesman for Arts, deputy manager of opposition business
Kate Ellis - opposition spokeswoman for Education, opposition spokeswoman for Early Childhood
Joel Fitzgibbon - opposition spokesman for Agriculture
Gary Gray - opposition spokesman for Resources, opposition spokesman for Northern Australia, shadow Special minister of State
Catherine King - opposition spokeswoman for Health
Jenny Macklin - opposition spokeswoman for Families and Payments, opposition spokeswoman for Disability Reform
Richard Marles - opposition spokesman for immigration and Border Protection
Shayne Neumann - opposition spokesman for Indigenous Affairs, opposition spokeswoman fo Ageing
Brendan O'Connor - opposition spokesman for Employment and Workplace Relations
OUTER SHADOW MINISTRY
Bernie Ripoll - opposition spokesman assisting the leader for Small Business
Claire Moore - opposition spokeswoman for Women, opposition spokeswoman for Carers, opposition spokeswoman for Communities, manager of opposition business in the Senate
Don Farrell - opposition spokesman for the Centenary of Anzac, opposition spokesman for Veterans' Affairs
David Feeney - opposition assistant defence minister, opposition spokesman for Justice
Julie Collins - opposition spokeswoman for Regional Development and Local Government, opposition spokeswoman for Employment Services
Andrew Leigh - shadow Assistant Treasurer, opposition spokesman for Competition
Bernie Ripoll - opposition spokesman for Financial Services and Superannuation, opposition spokesman for Sport
Sharon Bird - opposition spokeswoman for Vocational Education
Michelle Rowland - opposition assistant minister for communications, opposition spokeswoman for citizenship and multiculturalism
Melissa Parke - opposition assistant health spokeswoman
Jan McLucas - opposition spokeswoman for Mental Health, opposition spokeswoman for Housing and Homelessness
Doug Cameron - opposition spokesman for Human Services
SHADOW PARLIAMENTARY SECRETARIES
Julie Owens - small business, education
Jacinta Collins - shadow cabinet secretary, shadow parliamentary secretary to the leader
Michael Danby - shadow parliamentary secretary to the leader, arts
Jim Chalmers - shadow parliamentary secretary to the leader, trade and investment
Matt Thistlethwaite - foreign affairs, immigration
Gai Brodtmann - defence
Stephen Jones - regional development and infrastructure
Warren Snowdon - external territories, northern Australia, indigenous affairs
Ed Husic - treasurer
Louise Pratt - environment, climate change and water
Tony Zappia - manufacturing
Lisa Singh - attorney-general
Amanda Rishworth - health
Carol Brown - families and payments
Helen Polley - aged care
Source: Leader of the Opposition
