At the beginning of each round, each group (or individual) will roll a d6 for initiative. This represents when in the segment the action will occur (thus the low roll goes first). Normally, PCs will roll individually and each like-group of DM-controlled opponents will roll for the group. (e.g. One roll for the goblins and one roll for the bugbears, although the DM may simply roll one for all.)
The initiative result is only used for breaking ties where simultaneous action occurs. i.e. Two creatures that act on the same segment (and where it's important to know who acts first).
Dexterity Modifier. Any bonus (expressed by subtracting the number from the die roll) or penalty (expressed by adding the number from the die roll) for reaction due to Dexterity will have a corresponding effect on the initiative result. Results under 1 or over 6 are simply used to break ties.
Other Modifiers. Certain other effects or abilities will modify the initiative die. These will be detailed under the ability or the effect/item.