No, a monk can't use their Martial Arts feature with improvised weapons. Monk weapons are:
short swords and any simple melee weapons that don’t have the two-handed or heavy property.
Unfortunately, simple melee weapons are weapons that are in the "Simple Melee Weapons" category on the weapons table, and improvised weapons aren't present there. (Otherwise everyone who was proficient with simple melee weapons would be proficient with improvised weapons.)
So improvised weapons aren't simple melee weapons, and therefore they aren't monk weapons either and can't be used with Martial Arts.
Replacing a claw attack with an unarmed strike
Sorry, but no. Unarmed strikes use a weird hybrid of the rules for manufactured and natural weapons, but for the purposes of full-attacks, they work like manufactured weapons. That is, you get iteratives with them, but if you can only combine them with natural weapons by making those natural weapons secondary (−5 attack penalty, only ½Str to damage).
The first rule that you quote is specifically about spells and effects. A full-attack is not either of those.
Claws and lack of offhand unarmed strikes
Feral Combat Training does mean that anything from the monk’s unarmed-strike-improving class features can apply to natural weapons, and that can include the bit about never being offhand.
However, claws and other natural weapons are never “offhand” to begin with. The term “offhand” only applies when using two-weapon fighting, and that combat option does not interact with natural weapons (aside from the attack penalty, which applies to all attacks). So the fact that the monk class feature, combined with Feral Combat Training, says that natural weapons are never offhand does not do anything because that was already true.
Instead of “main hand” and “offhand,” natural weapons are either “primary” or “secondary.” These are different. When combined with manufactured weapons (or unarmed strikes) in a given full-attack, all natural weapons are secondary: they receive the −5 penalty and get only ½Str to damage. Neither the monk class nor Feral Combat Training does anything about treating them as secondary or removing or reducing the penalties for being secondary.
So whether you have Feral Combat Training or not, your full-attack using unarmed strikes is:
Unarmed Strike, Claw (−5), Claw (−5), Claw (−5)
If you have Feral Combat Training, the claws do benefit from the improved base damage dice of unarmed strike, however, even if they’re still stuck with ½Str to damage.
Two-Weapon Fighting, Feral Combat Training
If you are actually using two-weapon fighting, the provision about monks never having offhand unarmed strikes meaningfully applies only to the unarmed strike. It “applies” to the claws, but does nothing for them.
So, for example, if your two weapons are a sai and an unarmed strike, and you have the Two-Weapon Fighting feat, your attack routine would be:
Sai (−2), unarmed strike (−2), claw (−5), claw (−5)
The unarmed strike would add your full Strength to its damage, however. Note that I assumed that the sai took up one of your claw-hands. I did not wish to get into the debate about whether one can use two unarmed strikes as part of two-weapon fighting.
You didn’t ask, but about Flurry of Blows
All of the statements above about full-attack apply equally well to flurry of blows, except that you need Feral Combat Training to use natural weapons in a flurry at all, and flurry of blows cannot be combined with two-weapon fighting because of Paizo nonsense.
Personal recommendation
For the record, monks, natural attacks, and how they combine, these are some of the worst things in Pathfinder. The rules are confusing, complicated, and the result works very poorly. I suggest you save yourself a headache and just... not.
Best Answer
A Monk of Empty Hands does not take the -4 nonproficiency penalty for improvised weapons.
James Jacobs, Paizo creative director, clarifies this on the Pathfinder RPG forums:
Thus, you don't need to take Catch Off-Guard at all, not even for Improvised Weapon Mastery since you don't need to meet requirements for Monk bonus feats.