Whereas Situational Awareness concerns itself with the present situation, Reconnaissance concerns itself with anticipating and preparing for upcoming developments.
In Hisec, NPC-corp alts can be used for scouting in a capsule/rookie ship/shuttle since it is unlikely that the enemy would be willing to get CONCORDed over such a low-value target. Just make sure your implants are none or expendable so that you lose little if anything when podded.
As Warp Disruption Spheres (ie. “Bubbles”, Interdiction, etc) can only be used in nullsec, it is relatively painless to break through gate campers on both sides of a gate connecting two hisec/lowsec systems. Whenever you are in nullsec and you want to jump to an adjacent lowsec/hisec system, you only need to watch for warp bubbles on your end of the gate, as there will not be any on the other side. A fleet bumrushing gate campers may lose a few in the process (due to warp jamming), but the majority of the fleet will be able to escape intact.
Some ships such as Covert Ops and Recon ships have bonuses to cloaking and/or are immune to directional scanning. Cloaked ships are completed undetectable unless they are decloaked or bumped into (which would force them to uncloak). Ships that are immune to D-Scanning can still be located with the use of Combat Scanner Probes, however. Ships capable of equipping advanced cloaking devices (such as the Covert Ops Cloaking Device II) will be able to warp while cloaked, making them virtually invulnerable as long as you don’t run into anybody or anything. Fortunately, hitting an interdiction sphere does not force you to decloak, so it is entirely possible to sneak through it without detection. Using a cloak ensures you can monitor a gate without alerting the enemy to your presence. Just make sure you move from your arrival position, as any other ship arriving at the exact same position will bump you and cause you to uncloak.
Scouting ahead is the most fundamental reconnaissance activity. It ensures that no enemies are (immediately) present along a series of waypoints, so that the fleet can travel to the destination in relative safety. Scouting ahead could be performed in an expendable ship (eg. rookie ship, shuttle, cheap combat frigate).
When scouting uncloaked, it may be desirable to approach objects at 100km so that if there are in fact enemies camping there you have the opportunity to warp away and save yourself, or perhaps check other routes for safety. Of course, the enemy might anticipate this and attempt to relocate to the alternate stargate itself. Your commander and the scouts need to decide how to approach these situations; sometimes the best course of action is to simply come back to where you came from.
The enemy isn’t just going to be present where you’re headed – they will attempt to flank you from the sides or ambush you from behind. Whenever possible, a fleet should have scouts on the other sides of the adjacent systems just to watch for incoming traffic and get advance notice necessary to effectively relocate and regroup your fleet