Secretary of State George P. Shultz and Soviet Foreign Minister Eduard Shevardnadze will sign an agreement at the White House Tuesday setting up "nuclear risk reduction centers" in Washington and Moscow to decrease the chance of accidental war, administration officials said yesterday.

The agreement is the culmination of a four-year effort started by Sens. Sam Nunn (D-Ga.) and John W. Warner (R-Va.) to improve U.S.-Soviet communications about potentially threatening military activities. Negotiations between officials of the two nations on setting up the centers were completed this May in Geneva, with the U.S. team headed by then-assistant secretary of defense Richard N. Perle.

The Washington risk reduction center is to be staffed by Americans and the Moscow center by Soviets. The senators' original proposal called for centers with a mixture of both nationalities and more extensive responsibilities.

President Reagan last May hailed the agreement as "a practical measure that will reduce the risk of conflict between the United States and the Soviet Union, particularly nuclear conflicts that might result from accident, misinterpretation or miscalculation."

Officials said signing of the risk reduction accord is one of the few nearly certain outcomes of next week's Washington visit by Shevardnadze, which is expected to center on outstanding details of a treaty eliminating medium- and shorter-range missiles from Europe and elsewhere. The signing of such a treaty, if and when completed, is expected to be the occasion for a visit to Washington by Soviet leader Mikhail Gorbachev, perhaps late this year.

Officials gave some details yesterday of recent U.S. requests to Moscow regarding emigration of Soviet citizens and other human rights questions, which also are on the U.S. agenda for discussion at next week's talks.

While welcoming the news this week that 15 prominent Soviet Jews have been given permission to emigrate, Shultz and other State Department spokesmen called for action by the Soviet Union to set up "less arbitrary" and more systematic procedures for deciding such cases.

Many of those being permitted to emigrate now had been previously barred from going abroad because the Soviets contended that they had possessed state secrets, and therefore could not be permitted to leave.

The United States proposed in July in Stockholm that possession of secrets not be a bar to emigration and that, in case it is used as a bar, applicants be permitted to leave no more than one year after they have left posts where they had access to secret information.

U.S. sources said Soviets officials have been reminded that Gorbachev, during a visit to Paris in October 1985, said on television that possessors of state secrets should not be barred from emigration for more than five or 10 years. The sources said, however, that some Soviet citizens have been refused emigration for much longer on grounds of having secret information.

Among other recent U.S. requests, officials said, are for legalization of Hebrew teaching, scrutiny of new Soviet legal code provisions touching political and religious activity and reversal of a recent Soviet ruling that only immediate relatives of those who have emigrated are eligible to apply to join the move abroad.

A senior U.S. official said the Soviets also have been asked to agree to regular meetings of the two nations' diplomats to discuss human rights cases. Staff writer A.D. Horne contributed to this report.