Slovenia actually began brightly, and threatened to take a surprise lead in the third minute.
Playmaker Zlatko Zahovic whipped in an excellent near-post corner and Aleksander Knavs' close-range header almost found its way through, but Iker Casillas was alert to the danger and saved well.
The World Cup's greatest over-achievers were by no means overawed by the competition's under-achievers and initially proved more than a match - physically if not technically.
Given the nature of Srecko Katanec's game-plan, the Slovenes defended in numbers and looked to the pace of Mladen Rudonja on the left to launch their attacks.
For Spain, Javier De Pedro and Valeron bossed the midfield, winning free-kicks at will.
De Pedro went close twice in quick succession, using the new light-weight ball to his advantage.
Slovenia probed, but ultimately could not penetrate the Spaniards, who had begun to exert their authority on proceedings.
It came as no surprise when Spain opened the scoring and the source of the goal was even less of a shock.
Raul became the joint second-highest goalscorer in Spain's history on 26 goals with a strike that highlighted his predatory instincts.
Excellent work by Luis Enrique, plus a couple of ricochets, saw the ball go to Raul in the area and, with a deft shift in direction, the Spain striker fired in the opener.
After the break, Katanec's introduced Cimirotic for the ineffective Milan Osterc.
And the Slovene striker's first notable act was to get booked for a deliberate dive. But he also added some much-needed spark into a flagging side and struck a couple of venomous shots.
However, Spain extended their advantage with a superbly-worked move that saw De Pedro produce the cross of the tournament so far to find Valeron unmarked in the area and he converted with clinical precision.
But Jose Camacho's side were forced to hang on towards the end, when Cimirotic reduced the deficit to just one, applying a good finish after a one-two with substitute Milenko Acimovic.
Hierro then sealed the points with a late penalty - won rather dubiously by substitute Fernando Morientes - and consolidated his position as Spain's top scorer with 28 goals.
Spain: Casillas, Juanfran (Romero 83), Puyol, Hierro, Nadal,
Baraja, Luis Enrique (Helguera 74), De Pedro, Valeron, Raul,
Tristan (Morientes 67).
Subs Not Used: Albelda, Contreras, Curro Torres, Joaquin,
Luque, Mendieta, Ricardo, Sergio, Xavi.
Goals: Raul 44, Valeron 74, Hierro 88 pen.
Slovenia: Simeunovic, Milinovic, Galic, Knavs,
Novak (Gajser 77), Ales Ceh, Karic, Zahovic (Acimovic 63),
Pavlin, Osterc (Cimirotic 57), Rudonja.
Subs Not Used: Bulajic, Nastja Ceh, Dabanovic, Nemec, Pavlovic,
Sankovic, Tavcar, Tiganj, Vugdalic.
Booked: Karic, Cimirotic.
Goal: Cimirotic 82.
Referee: M Guezzaz (Morocco).