if you're talking about a cover song then you can have both guitars playing the same thing (ex. avenged sevenfold has parts in some of their songs where one guitar is used but live they both play the same chords/riff like in the main riff of "critical acclaim")
live vid. of a7x "critical acclaim":
http://www.youtube.com/watch?v=wDtrYMCCM…
if it's a song you wrote then you could probably add another part to it.
or the third option is to take the creative road if your doing a cover song and add another part to make it your own (a good example of this is the rock cover version of "apologize" (covered by silverstein))
for this you could add a completely different part or add different chord voicings (where two chords composed of the same notes but in either a different position or place on the neck)
vid. for "apologize" cover:
http://www.youtube.com/watch?v=q8CxOA1D7…
ecample of a jazz chord voicing for Gmaj7:
type a type b
e|-------------|-------|
b|----3-------|---12-|
g|----4-------|---11-|
d|----4-------|---12-|
a|----x-------|---10-|
e|----3-------|--------|
and one guitar would play type a and the other would play type b.
you can also play power chords over major and minor chords.
another thing i can think of is if one guitar plays a power chord then you can add an octave chord to make the technical major or minor chord.
example:
PC OC
e|---------|---------|
b|---------|---------|
g|----5---|----9---|
d|----5---|----x---|
a|----3---|----7---|
e|---------|---------|
the PC (power chord) is a C5 and the octave is an E. together they complete the arpeggio for a Cmajor. When you do this it helps to stay in the key or the progression won't sound right.
also in "critical acclaim"
the final choice for lead parts is harmonizing (i'm not demonstrating that).
lesson on harmony:
http://www.ultimate-guitar.com/lessons/g…
songwriter, musician, and guitar player for O.S.A.S.