The initiative rules for the surprise round may modify this a little.
If you are acting in the surprise round, you could cast Cat's Grace on an ally who didn't make the Spot check. When the regular round starts and everybody else rolls initiative, your buddy gets +2.
You can also lob a net or a tanglefoot bag at a surprised enemy. When he finally rolls Init, an entangled opponent takes a -4 penalty to his Dex due and therefore -2 on Init. Various spells make opponents entangled or impose a Dex penalty, too.
SRD
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Combat is cyclical; everybody acts in turn in a regular cycle of rounds. Combat follows this sequence:
1. Each combatant starts out flat-footed. Once a combatant acts, he or she is no longer flat-footed.
2. Determine which characters are aware of their opponents at the start of the battle. If some but not all of the combatants are aware of their opponents, a surprise round happens before regular rounds of combat begin. The combatants who are aware of the opponents can act in the surprise round, so they roll for initiative. In initiative order (highest to lowest), combatants who started the battle aware of their opponents each take one action (either a standard action or a move action) during the surprise round. Combatants who were unaware do not get to act in the surprise round. If no one or everyone starts the battle aware, there is no surprise round.
3. Combatants who have not yet rolled initiative do so. All combatants are now ready to begin their first regular round of combat.
4. Combatants act in initiative order (highest to lowest).
5. When everyone has had a turn, the combatant with the highest initiative acts again, and steps 4 and 5 repeat until combat ends.
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