Guadio is backed as the de facto leader by more than 40 nations, including the USA and major European powers, who want Maduro to step down.
But US officials have conceded that their most realistic option is to persuade members of the Venezuelan military to defy Maduro's order to block the aid.
Venezuelan armed forces officers and troops have the opportunity to participate in a humanitarian campaign that would help alleviate severe problems in their country, which is suffering from widespread shortages of food and medicine and hyperinflation, Kevin Whitaker said in the Colombian border city of Cucuta.
"Inhibiting the entry of this aid could be seen as a crime against humanity".
Meanwhile, Venezuela's communications minister, Jorge Rodriguez, appeared on state TV claiming Colombian intelligence, the CIA and exiled Venezuelan opposition lawmaker Julio Borges were behind a plot to overthrow Maduro.
"We are working to coordinate the distribution of aid now, but we need Trump to continue his pressure on the military", he said.
Venezuelan President Nicolás Maduro blocked American aid from reaching the country this week, accusing the USA of trying to smuggle weapons to opposition factions and using the offer of aid to suggest he was unable to care for his people's needs.
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China, Iran, Russia and Turkey have put their weight behind Maduro.
But the administration has stopped short of imposing so-called "secondary" sanctions, which would punish non-U.S. companies for doing business with the Venezuela government or the state oil monopoly PDVSA.
Mr Guaido, the country's National Assembly chief, says the May 2018 vote in which Mr Maduro won a second six-year term was a sham. They squeeze us by the neck and then make us beg for crumbs'.
Humanitarian organizations have warned that attempting to force the aid into the country would be unsafe, and a top US official on Thursday said Washington did not plan to do so.
Guaido's representative in Cucuta, Lester Toledo, said the provisions already delivered were the "first drops" and promised "a tsunami of humanitarian aid" would follow.
He told the cheering crowd: 'We will keep going until we achieve our objective'.
While criticizing Maduro for his crackdown on protesters and other abuses, progressive lawmakers in the USA have denounced the Trump administration's interference in Venezuela's internal political affairs.
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He claims his legitimacy from the constitution, but Maduro - labeled a dictator by the West and his Latin American neighbors - insists his re-election past year was constitutional.
The embattled Venezuelan leader dug in further Friday, contending the aid is part of a coup being orchestrated by the USA government.
Ministry spokeswoman Hua Chunying's statement came in response to a question about a meeting on Thursday of an "International Contact Group" led by Uruguayan president Tabare Vazquez and attended by leaders of 14 countries, including Spain, Italy, Portugal and Sweden.
Turning his ire on the Contact Group, Maduro fumed: "You don't listen to the truth in Venezuela.
If they really wanted to help they should lift all the economic sanctions, the financial persecution, and cancel the economic ban that robs us of billions of dollars", Maduro said.
Maduro, who last weekend rejected an European Union ultimatum to organize snap presidential elections, said he would welcome the mission.
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In 1912, textile workers in Lawrence, many of them immigrant women, walked off the job and went on strike to protest wage cuts. After the rally, Warren headed to Dover, N.H., a town of 32,000 with a long history in now-faded industries like shipbuilding.
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