Once again, I'm a Melee player but this is the regiment that I do daily.
5min warmup. Go into training mode and do basic movement. For melee this would include dashdancing, wavedashing, shorthopping, wavelanding on platforms. Making sure my movement is crispy and I'm doing exactly what I want.
10-20min techskill practice. Usually there are several techniques that I want to get more consistent at or learn. This (for me) includes ledge stuff, shield drops, needle stuff, and out of shield options.
~30min combo practice. I load up a low level computer and combo the shit out of it, making sure my followups become automatic. I usually do this until I get bored. I generally practice my combos mainly on top tier characters unless I notice that my punishes on other characters is lacking (usually from getting bopped by someone in tournament)
Watching top level matches is vital. Check out top players that play your character and watch what they do. I find its helpful to watch videos in slow motion to fully understand the things they're doing. If I see something I want to incorporate into my gameplay, I take a mental note and then try it out in practice, then friendlies.
Hopefully that applies to smash 4